JP2001207123A - Film having high hardness and high droplet slidability and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film structure having both droplet slidability and hardness, to provide a method for producing the same, and to provide a coating material. SOLUTION: This coating material comprises a solution or emulsion obtained by adding, to a solvent, a metal alkoxide and/or a sol having a primary particle diameter of <=100 nm and a substance having characteristics which phase-splits from the above components and decomposed, burns or sublimes at a temperature of room temperature to 700 deg.C. The film having high hardness and high droplet slidability is obtained by coating a substrate with the coating material, thermally treating the coated substrate in a temperature range of room temperature to 700 deg.C to form the primary layer having many fine holes having an average hole diameter of 100 nm to 2 μm, and then coating at least one portion of the primary layer with a water-repelling agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a membrane structure which is easy to control the structure and has both excellent water sliding property and hardness, a method for producing the same, and a coating material used therefor.

[0002]

2. Description of the Related Art Many water-slidable surfaces have been conventionally obtained by treating the surface with silicon, fluorine, or the like. The water-slidable surface obtained by such a conventional technology has a contact angle with water of 100%. The drop angle of the droplet was about 50 to 60 ° for a 20 mg droplet. This treatment has already been put to practical use for clothing, car glass, painted surfaces and the like.

On the other hand, by providing a low-energy surface with an appropriate structure, the contact area between the surface and water can be remarkably reduced, and a very high water repellency (super repellency) having a contact angle of 150 ° or more. (Aqueous) are known to be obtained. And if this super water repellent surface shows high water slippage as it is, it is expected to be highly effective for various purposes such as snow and raindrop prevention, stain prevention, rust prevention, electrical insulation, mold release properties, etc. Can be.

[0004] However, there is no simple correlation between the property of super water repellency and the property of water droplets falling (sliding property). (In order to reduce the resistance between the surface and the water to such an extent that the water droplets fall down), it is not sufficient that the surface has super water repellency.

[0005] From the above, the inventors of the present invention have conducted a study to impart a high water-sliding property to a surface such that a water droplet falls down even if the inclination is only a few degrees. By adopting such an uneven structure, a film (super water-repellent film) having a high water-sliding property enough to cause water drops to fall even with a tilt of only about 1 degree has been successfully obtained (Japanese Patent Application No. 11-110).
294636).

[0006]

However, in order to obtain such a super water-repellent film, it is basically necessary to form a fine uneven structure on the surface. The hardness of the film itself is reduced, which delays the practical use of the super water-repellent film.

[0007] The present invention has been made in view of the above problems, and an object of the present invention is to provide a membrane structure which is easy to control the structure and has both excellent hardness and water slidability, and a method of manufacturing the same. Another object of the present invention is to provide a coating agent used in the production method.

[0008]

Means for Solving the Problems To achieve the above object, in the present invention, an average pore diameter of 100 nm or more is used.
It is characterized in that a microporous underlayer having a large number of micropores of 2 μm is formed using phase separation, and a water-repellent treatment is applied to the underlayer to produce a high hardness and high water-sliding film.

Further, in the present invention, in order to further improve the super water repellency, the surface of the base material is formed by a first uneven surface formed with the first surface roughness and a first unevenness formed by the first surface roughness. Formed on the first uneven surface with a small second surface roughness
This is characterized in that a high hardness and high water-sliding film is produced by performing a water-repellent treatment on this underlayer. In forming the surface having the double surface roughness, the first uneven surface is formed by using the same phase separation as described above, and the second uneven surface is formed by using finer dispersed phase or fine particles. A surface can be formed.

As a method for producing a high hardness and high water-sliding film satisfying such requirements, for example, a metal alkoxide and / or a sol having a primary particle diameter of 100 nm or less are separated from these in a solvent, and the temperature is reduced from room temperature to 700 ° C. A substance having the property of decomposing, burning, and sublimating at a temperature of up to 100 ° C. forms a solution or an emulsion added to a solvent, and then forms a film at room temperature (room temperature) using the solution. A method in which the above-mentioned substance is removed by keeping the substance at a certain temperature for a certain period of time can be used. Further, it is possible to satisfy the above-mentioned requirement by mixing particles having different sizes (particle diameters) or controlling the aggregation diameter of the particles.

For the water repellent treatment, it is possible to use a fluorine or silicone water repellent or a combination thereof as appropriate. In order to impart self-cleaning properties to the high hardness and high water-sliding film according to the present invention, a photocatalyst can be contained in the porous underlayer.

More specifically, the present invention provides the following.

(1) A high-hardness and high-slidability film having both practical hardness and high-slidability.

(2) A high hardness and high water-sliding film having the following characteristics. Contact angle is 140 ° or more, falling angle of 7mg droplet is 30 °
Below, and hardness is 3H or more in pencil hardness. The falling angle is preferably 20 ° or less, more preferably 15 ° or less. As for the hardness, the pencil hardness is preferably 5H or more, more preferably 6H or more in pencil hardness. It is to be noted that both the falling angle and the hardness can be achieved by applying the present invention.

(3) An average pore diameter of 100 nm to 2 μm on the surface
(1) or (2), which is a highly water-slidable film provided with a microporous layer having a large number of micropores.

(4) A high-hardness, highly water-slidable film comprising a microporous layer having a surface subjected to a water-repellent treatment and having a large number of micropores having an average pore diameter of 100 nm to 2 μm.

(5) The high hardness and high water-sliding film according to any one of (1) to (4), which is a transparent film.

(6) Average pore size 1 formed using phase separation
A high-hardness, high-water-sliding film comprising a porous underlayer having pores of 00 nm to 2 μm and a transparent water-repellent layer formed on at least a part of its surface.

(7) A first uneven surface formed with a first surface roughness, and a second uneven surface having a smaller surface roughness than the first surface roughness.
A high hardness and high water-sliding film formed on a surface having a double surface roughness with a second uneven surface formed on the first uneven surface with a surface roughness of 1.

(8) The first surface roughness is 100 nm to 2 μm
m, wherein the second surface roughness is less than 100 nm. Although the lower limit of the second surface roughness is not particularly limited, a surface that further enhances super water repellency by interposing air in a concave portion due to the surface roughness,
From the viewpoint of practically forming the second surface roughness by using the phase separation and the inclusion of fine particles, the lower limit of the second surface roughness is about 1 nm, and more preferably about 3 nm.

(9) The first uneven surface is formed using phase separation, and the second uneven surface is formed using phase separation or contained particles (7) or (7). 8) A high hardness and high water-sliding film according to 8).

(10) The first uneven surface is formed by using particles or aggregated particles having a larger particle diameter, and the second uneven surface is formed by using particles or primary particles having a smaller particle diameter. The high hardness and high water-sliding film according to (7) or (8), which is formed by the above method.

(11) The transparent film (7) to (1)
0) The high hardness and high water-sliding film according to any of 1).

(12) The high hardness and high water-sliding film according to any one of (7) to (11), wherein a water-repellent layer is formed on at least a part of the surface.

(13) The high hardness and high water-sliding film according to any one of (1) to (12), wherein the photocatalyst is dispersed.

As described above, by dispersing the photocatalyst (typically, titanium oxide) (preferably, dispersed in a microporous underlayer), the high hardness and high water-sliding film of the present invention has a self-cleaning property ( (Japanese Patent Application No. 11-294637).

(14) A high hardness and high water-sliding property comprising a phase separation formed by a raw material liquid for the membrane base material, a predetermined solvent, and a substance removed after the raw material solution for the membrane base material is solidified. Stock solution of coating agent for film formation.

In the present invention, this stock solution is dissolved in a predetermined solvent to prepare a coating agent for forming a high hardness and high water-sliding film (a specific embodiment is described in (15) below).
To (18)). Here, the “raw material liquid of the membrane base material” is capable of forming a phase separation with other components, and may give practical hardness to the finally obtained water-slidable membrane. Any material that can be used may be used. An example is a metal alkoxide used as a raw material for the sol-gel method. Further, the “substance removed after the raw material liquid of the film base material is solidified” may be from room temperature to 70%.
Substances that have the property of being removed at temperatures up to 0 ° C. (especially
(A substance having the property of decomposing, burning, and sublimating at a temperature from room temperature to 700 ° C.).

(15) A phase separation between the metal alkoxide and the metal alkoxide in a predetermined solvent, and
A coating material for forming a high hardness and high water-sliding film, comprising a solution or an emulsion obtained by adding a substance having a property of being removed at a temperature of up to ° C to a solvent.

(16) A metal alkoxide, a sol having a primary particle diameter of 100 nm or less, and a substance which has a property of phase separation with a sol having a primary particle diameter of 100 nm or less and being removed at a temperature from room temperature to 700 ° C. A coating agent for forming a high hardness and high water-sliding film, comprising an added solution or emulsion.

The term “characteristics removed at a temperature from room temperature to 700 ° C.” means, for example, a characteristic of decomposing, burning, and sublimating at such a temperature, and a substance group having such characteristics (for example, A substance that can form a phase separation with other components is appropriately selected from among a group of thermal sublimable substances). These include organic polymers, which generally decompose and burn with heat
And those which are insoluble in metal alkoxides and soluble in a predetermined solvent such as ethanol or ethyl acetate.

(17) The coating agent according to (16), wherein the sol comprises a colloidal silica sol.

(18) A dispersion diameter in a phase-separated state of 100 n, which has a characteristic of being phase-separated from a metal alkoxide in a predetermined solvent and being removed at a temperature from room temperature to 700 ° C.
A coating material for forming a high hardness and high water-sliding film, comprising a solution or an emulsion in which a substance having a particle size of at least m and a substance having a particle size of less than 100 nm are added to a solvent.

(19) After applying the coating agent according to any one of (15) to (18) on a substrate, a heat treatment is carried out in a temperature range from room temperature to 700 ° C. to form a microporous underlayer. A method of forming a high hardness and high water-sliding film on the substrate by applying a water repellent to at least a part of the underlayer.

Further, in the present invention, it is also possible to apply a coating agent containing particles of different sizes as described below, and a method of forming a high hardness and high water-sliding film using the coating agent.

(20) A coating agent for forming a high hardness and highly water-slidable film, comprising particles or aggregated particles having a particle diameter of 100 nm or more and particles or primary particles having a particle diameter of less than 100 nm.

(21) The coating agent according to the above (20) is applied to a substrate, and the coating agent having the first surface roughness formed of particles or aggregated particles having a particle diameter of 100 nm or more is formed. (1) a second uneven surface formed on the first uneven surface with a second surface roughness smaller than the first surface roughness formed by particles or primary particles having a particle diameter of less than 100 nm; A method of forming an underlayer having a surface having a double surface roughness with an uneven surface, and applying a water repellent to at least a part of the underlayer to form a high hardness and high water-sliding film on the substrate.

Further, in the present invention, the following method can be adopted. (22) A method for producing a highly water-slidable film by subjecting a surface of a microporous layer having a large number of micropores having an average pore diameter of 100 nm to 2 μm to a water-repellent treatment.

(23) A first uneven surface having a first surface roughness, and a second uneven surface formed on the first uneven surface with a second surface roughness smaller than the first surface roughness. A method of producing a highly water-slidable film by subjecting a substrate surface having a double surface roughness to a surface to a water-repellent treatment.

(24) The first uneven surface has a surface roughness of 100 n
m to 2 μm, and the second uneven surface has a surface roughness of 100 nm.
The method according to (23), which is less than.

(25) The method according to any one of (19) to (24), wherein a fluorine-based water repellent is applied.

(26) By using the coating agent according to any one of (15) to (18), adjusting the state of the phase separation and / or adjusting the heat treatment step, the water-sliding property finally obtained. A method for adjusting the slipperiness strength and / or the hardness of the membrane.

[0043]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments will be described specifically and in detail to facilitate understanding of the present invention. In order to obtain good slipperiness, the difference between the advancing contact angle (contact angle on the advancing side of the droplet) and the receding contact angle (contact angle on the retreating side of the droplet) when the droplet falls on an inclined surface It is desirable to reduce the roughness of the film by providing a certain roughness,
It is effective to make the surface water-repellent to increase the contribution of air entrapment (Johnson Jr., RE & Dettre,
RH Contact Angle Hysteresis, I. Studyof an Ide
al Rough Surface, Adv. Chem. Ser., 43, 112-135, (1
963)).

Specifically, it is most desirable to make the surface structure acicular in order to obtain good lubricity, but such a structure cannot maintain the surface hardness. In view of the above, the present inventors have conducted intensive studies on the structure of the film surface in order to maintain the slipperiness and water repellency, and to give the film a practical hardness. And / or a solution or an emulsion in which a sol having a primary particle diameter of 100 nm or less and a substance which is separated from these in a solvent and which has a property of decomposing, burning, and sublimating at a temperature from room temperature to 700 ° C. were added to the solvent was prepared. . And
After forming a film at room temperature using this, from room temperature to 700 ° C.
By maintaining for a certain period of time at a temperature of up to 100 μm, a microporous structure having a large number of micropores having an average pore diameter of 100 nm to 2 μm due to phase separation is formed. It has been found that a film excellent in point can be produced.

Since the film obtained by the present invention is a microporous film, high hardness can be obtained without impairing the slipperiness and water repellency. The structure of the film may be a combination of a plurality of substances as long as the size and solubility conditions are satisfied.

The material of the film usable in the present invention is mainly an inorganic material, but may be an organic material as long as it has appropriate hardness and heat resistance. The method for producing the film is mainly a wet method such as spin coating, dip coating, and spraying. A substance that decomposes, burns, or sublimates at a temperature from room temperature to 700 ° C. is not limited to an inorganic substance or an organic substance.

In the present invention, the first uneven surface is formed on the surface of the substrate by, for example, the same method for forming a porous layer as described above, and the second uneven surface is further finely formed on the first uneven surface. A surface having the formed dual surface roughness can also be formed. With this structure, it is possible to simultaneously achieve high surface hardness while forming a finer air intervening layer to further enhance water repellency. As a method of achieving the second surface roughness for forming the second uneven surface, a method of forming by containing fine particles such as colloidal silica, and a method of separating phases with a finer dispersion diameter than the above-described phase separation. A method can be employed in which the substance is removed by decomposition, combustion, or sublimation to provide a finer porous structure.

[Water Repellent] As the water repellent, it is possible to use fluorine or a silicone-based water repellent or a combination thereof. However, those containing fluorine have a large effect of lowering the surface energy. And fluoroalkylsilane is particularly preferred. In addition, surface treatment agents such as perfluoroalkyl carboxylic acids, perfluoroalkyl sulfonic acids, and perfluoroalkyl phosphoric acids, oligomers containing perfluoroalkyl groups, and various fluorines represented by polytetrafluoroethylene (PTFE) Resins, graphite fluoride, pitch fluoride and the like can also be used.

For the water-repellent treatment, a wet method is most excellent in efficiency and cost as in the case of the microporous underlayer, but may be performed by a vapor deposition method or a sputtering method depending on the raw material.

[Photocatalyst] As a photocatalyst material that can be added, one or a combination of titanium oxide, tin oxide, zinc oxide, strontium titanate, tungsten oxide, iron oxide and copper oxide can be used. Examples of these precursors include various inorganic and organic compounds generated by heating these photocatalysts.For example, in the case of titanium oxide, titanium hydroxide, titanium alkoxides such as titanium tetrapropoxide, titanium chloride, titanium sulfide, Titanium bromide, titanium iodide, biscyclopentadienyl titanium, dicarbonylbiscyclopentadienyl titanium,
Chlorobiscyclopentadienyl titanium, dichlorobiscyclopentadienyl titanium, dimethylbiscyclopentadienyl titanium, trichlorocyclopentadienyl titanium, tetrabenzyl titanium and the like can be mentioned.

Here, as long as the composition of the film satisfies the conditions of size and solubility, a combination of a plurality of substances may be used. For example, a titanium oxide photocatalyst decomposes an organic water repellent. When the titanium oxide photocatalyst is put into the film, its concentration is adjusted to about 2 wt% (this will be verified in a later example) or silicon, aluminum, zirconium, etc. It is desirable to constitute the substrate with an oxide or hydroxide of the above or a mixture thereof, and to add the titanium oxide photocatalyst in an amount in the range of 0.5 to 60% by weight of these substrates. When the addition amount of the photocatalyst is larger than this, the photocatalytic activity increases, but the durability of the water repellent decreases, so that the contact angle decreases in a short time.

[Sliding Water] The super-water-repellent surface can significantly reduce the contact area between the surface and water. Static water repellency is evaluated by the contact angle, but in practice, dynamic water repellency, that is, slipperiness is more important. This is evaluated by the angle at which the droplet starts to fall when the flat surface is tilted (fall angle) and the difference between the advancing contact angle and the receding contact angle created by the droplet and the surface (hysteresis). Tend to value these indices more than contact angles. The falling angle of a droplet on a solid surface having a high contact angle is not always low, and a high falling angle may be exhibited despite a high contact angle. For example, FAS-17 (CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si
When (OMe) ₃ ) is coated, the water contact angle is about 105 °, and the falling angle with a 20 mg droplet is about 50 °,
Although the water contact angle of glass coated with methyltrimethoxysilane is as low as about 64 °, the falling angle of a 20 mg droplet is about 35 °, which is lower than that of FAS-17.

[Use] A film having both practical hardness and excellent water-slidability has not been obtained so far, but such a film is provided by the present invention.

The membrane according to the present invention having both practical hardness and excellent slipperiness can be used for the exterior of vehicles such as automobiles and Shinkansen, ship bottom paints, exterior lights, kitchen and kitchen appliances, bathrooms and washrooms and their accessories, Nets, buoys, dental supplies, electrical equipment, house floors and exteriors, entrance doors and knobs, roofs, pools and poolsides, piers, gates, posts, benches, towers, antennas,
Wires, garages, tents, umbrellas, raincoats, sporting goods and sports clothing, helmets, leather products such as shoes and bags, outdoor loudspeakers and audio equipment such as cameras, videos, paper, speakers, curtains, carpets, gas stations, etc. Lubrication nozzles, chemical plants such as refineries, metal tools,
A wide range of applications such as nails, screws, and buckets are conceivable.

[0055]

Embodiments of the present invention are described below.

In this example, the concentrations of the solvent, metal alkoxide and polymer were adjusted so as to fall within the phase separation region in the phase diagram of the ternary system shown in FIG. A phase separation was formed according to the scheme. The obtained phase separation was a heterogeneous system, and it is considered that, as shown in FIG. 3, a dispersion of polymer microparticles in a mixture of an alcohol (solvent) and an alkoxide dissolved was formed. It is also considered that the silica fine particles (for example, colloidal silica) forming the silica sol were further dispersed.

By heat-treating the coating material in the above phase-separated state, the coating material is solidified and the polymer is removed, and water-repellent treatment is performed. As a result, micropores as shown in FIG. A large number of surfaces (microporous surfaces) were obtained (SEM photograph). Note that the cross section of this micropore is shown in FIG.
It is considered that the substrate surface 2 having the crater-like micropores 1 as shown in FIG.

It is possible to obtain super water repellency only by the unevenness of the substrate surface due to the crater-shaped micropores 1 described above. However, by adding silica sol and containing fine particles such as colloidal silica, Further fine irregularities can be formed on the surface irregularities. This fine unevenness can be formed also by a method using a phase separation. Compared with the crater-like uneven dispersion forming polymer, a phase separation material having a finer dispersion diameter is contained, and it is subjected to heat treatment. It can also be formed by removing.

That is, as shown in the model diagram of FIG. 6, when only the first uneven surface 11 is formed on the surface of the base material 10 by the crater-like fine holes, for example, Although the slope 12 in the portion becomes a relatively flat surface, it exhibits excellent water repellency to the droplet 13.

On the other hand, as shown in the model diagram in FIG.
For example, when the finer second uneven surface 22 is formed on the surface of the base material 20 in addition to the first uneven surface 21 formed by the crater-shaped fine holes as described above, the liquid droplets 23 can be more excellently repelled. You will be able to demonstrate water.

Example 1 20 g of ethanol and tetraethyl orthosilicate (T
2 g of EOS) and 1.2 g of hydrochloric acid were mixed for 36 hours and hydrolyzed. On the other hand, the acrylic polymer was dissolved in ethanol to adjust the solid content to 5.4%. Then, this acrylic polymer / ethanol solution was added to the TEOS solution for 4 hours.
g, and then 4 g of ethanol, and then 0.12 g of silica sol (colloidal silica), to thereby prepare a coating solution. This coating solution is prepared by hydrolysis T
A phase separation in which the acrylic polymer was dispersed in the EOS ethanol solution was formed.

The phase-separated coating solution was spin-coated on Pyrex (registered trademark) glass at 1500 revolutions, and the coat-dry cycle was repeated 10 times.
It was baked for 0 minutes. The thus obtained film was subjected to a water-repellent treatment by coating a fluoroalkylsilane hydrolyzed with an equivalent amount of water by a thermal CVD method, thereby producing a water-slidable film.

The resulting water-sliding membrane has a crater-like microporous structure having an average pore diameter of 1 μm, and further has finer irregularities formed of colloidal silica thereon, and has a contact angle of 157 °. In this case, a 7 mg droplet had a falling angle of 6.5 ° and a high hardness and high water-sliding film having a pencil hardness of 8H.

Comparative Example 1 An ethanol solution of aluminum acetylacetone (2.
A cycle in which a sol in which 0.24 wt% of nitric acid-containing boehmite was dispersed on a pyrex glass was applied by spin coating on a Pyrex glass and baked on a hot plate at 500 ° C. for 20 seconds was repeated five times to produce a transparent film. . The transparent film was immersed in a 2% methanol solution of fluoroalkylsilane hydrolyzed with an equivalent amount of water for 40 minutes, dried at 140 ° C. for 20 minutes, and subjected to a water-repellent treatment to obtain a water-slidable film.

The obtained water-slidable membrane had an average pore diameter of 200 n.
m microporous structure with a contact angle of 155 ° C
However, the falling angle of the 7 mg droplet was about 30 °, and its hardness was 3B in pencil hardness.

Comparative Example 2 A coating agent having the same composition as the coating agent according to Example 1 was prepared alone except that the acrylic polymer was not added, and film forming and repelling were performed in the same manner as in the above Example. Water treatment was performed.

The obtained film was dense and transparent, the hardness was as high as 8H in pencil hardness, and the contact angle was 133 °, but it was 90 °.
Even when the film was tilted, the droplets of 7 mg did not fall down, and the water slip did not appear.

Example 2 Ethanol: 10 g, concentrated HCl: 0.6 g, tetraethyl orthosilicate: 1.0 g were mixed for 19 hours, and a commercially available silica sol having an affinity for methyl ethyl ketone (MEK) (particle size: 15 nm) was added. 1500 rpm
m and spin coating was performed. Example 1 by thermal CVD
When a water repellent treatment was performed in the same manner as in
A high-hardness super water-repellent film having a falling angle of 52 °, a drop angle of 7 mg of 30 ° and a pencil hardness of 3H was obtained. This film has a primary particle size of 15 nm.
Had a double roughness structure in which a 600 nm aggregated structure was formed secondarily. The SEM photograph is shown in FIG.

Comparative Example 3 Instead of the MEK-based silica sol of Example 2, an alcohol-based silica sol having excellent dispersibility in ethanol (particle size:
15 nm). As a result, the contact angle was only 131 °, and the 7 mg droplet did not fall even when tilted at 90 °.

[0070]

As described above, according to the present invention,
A highly rigid and highly water-slidable film having a controlled structure can be easily produced. This can be suitably used for various industrial products and contributes to a wide range of applications.

[Brief description of the drawings]

FIG. 1 is a diagram showing a phase diagram of a three-component system including a solvent, a metal alkoxide, and a polymer according to Example 1.

FIG. 2 is a diagram illustrating a scheme for forming a phase separation according to Example 1.

FIG. 3 is a diagram illustrating an assumed state of phase separation according to the first embodiment.

FIG. 4 is a diagram showing an SEM photograph of the surface of the microporous material obtained in Example 1.

5 is an imaginary view of a cross section of the microhole shown in FIG. 4;

FIG. 6 is a schematic sectional view schematically showing a substrate having only a first uneven surface.

FIG. 7 is a schematic cross-sectional view schematically showing a substrate in which a second uneven surface is formed on a first uneven surface.

FIG. 8 is a view showing an SEM photograph of a film surface obtained in Example 2.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Crater-shaped micro hole 2 Base material surface 10, 20 Base material 11, 21 First uneven surface 12 Slope of first uneven surface 13, 23 Droplet 22 Second uneven surface

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09K 3/18 104 C09K 3/18 104 // C09D 133/00 C09D 133/00 183/02 183/02 ( 72) Inventor Kazuhito Hashimoto 2073-2, Iijima-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture 213 New Building Hongodai D Building 213 (72) Inventor Akira Fujishima 710 Nakamaruko Nakahara-ku, Kawasaki City, Kanagawa Prefecture 5F F-term (reference) 4D075 AE03 BB28Z BB93Z CA02 CA34 CA36 CB06 CB33 DA06 DA23 DB01 DB13 DB14 DB16 DB18 DB20 DC01 DC08 DC11 DC15 DC18 DC24 DC38 EA07 EA13 EA43 EB16 EB22 EB42 EC01 EC03 EC08 EC53 4H020 BA32 BA36 4J038 CG141 DL021 DM021 HA446 JA16 JA07 MA06 NA07 MA07

Claims (26)

[Claims] 1. A high-hardness and high-slidability film having both practical hardness and high-slidability. 2. A high hardness and high water-sliding film having the following characteristics.
The contact angle is 140 ° or more, the falling angle of a 7 mg droplet is 30 ° or less, and the hardness is 3H or more in pencil hardness. 3. The highly hard and highly water-slidable film according to claim 1, wherein the highly water-slidable film is provided with a microporous layer having a large number of micropores having an average pore diameter of 100 nm to 2 μm on the surface. 4. An average pore size of 1 whose surface has been subjected to a water-repellent treatment.
A high-hardness, highly water-slidable film comprising a microporous layer having a large number of micropores of 00 nm to 2 μm. 5. The high hardness and high water-sliding film according to claim 1, which is a transparent film. 6. An average pore size of 100 formed using phase separation.
A high hardness and high water-sliding film comprising a porous underlayer having pores of nm to 2 μm and a transparent water-repellent layer formed on at least a part of its surface. 7. A surface having a first uneven surface formed with a first surface roughness and a first uneven surface formed with a second surface roughness smaller than the first surface roughness. A high hardness and high water sliding property film formed on a surface having a double surface roughness with the formed second uneven surface. 8. The method according to claim 1, wherein the first surface roughness is in a range of 100 nm to 2 μm, and the second surface roughness is less than 100 nm.
The high hardness and high water-sliding film according to claim 7. 9. The method according to claim 7, wherein the first uneven surface is formed by using phase separation, and the second uneven surface is formed by using phase separation or contained particles. 2. A high hardness and high water-sliding film according to item 1. 10. The first uneven surface is formed using particles or aggregated particles having a larger particle diameter, and the second uneven surface is formed using particles or primary particles having a smaller particle diameter. The high hardness and high water-sliding film according to claim 7 or 8, which is formed. 11. The high hardness and high water-sliding film according to claim 7, which is a transparent film. 12. The high hardness and high water-sliding film according to claim 7, wherein a water-repellent layer is formed on at least a part of the surface. 13. The high hardness and high water-sliding film according to claim 1, wherein a photocatalyst is dispersed. 14. A raw material liquid for a membrane substrate, a predetermined solvent, and
An undiluted solution of a coating material for forming a high hardness and high water-slidable film, which is obtained by forming a phase separation with a substance which is removed after the raw material liquid of the membrane base material is solidified. 15. A solution or an emulsion in which a metal alkoxide and a substance having a property of phase-separating with the metal alkoxide in a predetermined solvent and having a property of being removed at a temperature from room temperature to 700 ° C. are added to the solvent. , A coating agent for forming a high hardness and high water-sliding film. 16. A metal alkoxide having a primary particle diameter of 10
A sol having a hardness of 0 nm or less, and a substance having a property of phase separation with a sol having a characteristic of being removed at a temperature from room temperature to 700 ° C. in a predetermined solvent, comprising a solution or an emulsion in which the solvent is added. Coating agent for forming an aqueous film. 17. The coating agent according to claim 16, wherein the sol comprises a colloidal silica sol. 18. A substance having a dispersion diameter in a phase-separated state of at least 100 nm and a characteristic of being separated from a metal alkoxide and a predetermined solvent in a predetermined solvent and having a property of being removed at a temperature from room temperature to 700 ° C. A coating solution for forming a high hardness and high water-sliding film, comprising a solution or an emulsion obtained by adding a substance to a solvent. 19. A microporous underlayer is formed by applying the coating agent according to any one of claims 15 to 18 to a substrate and then performing heat treatment in a temperature range from room temperature to 700 ° C. A method for forming a high hardness and high water-sliding film on a substrate by applying a water repellent to at least a part of an underlayer. 20. A coating composition for forming a high hardness and high water-sliding film, comprising particles or aggregated particles having a particle diameter of 100 nm or more and particles or primary particles having a particle diameter of less than 100 nm. 21. A coating material according to claim 20, which is applied to a substrate, and formed by particles having a particle diameter of 100 nm or more or aggregated particles, and formed by a first surface roughness.
And second irregularities formed on the first irregular surface with a second surface roughness smaller than the first surface roughness formed by particles or primary particles having a particle diameter of less than 100 nm. A method for forming a high hardness and high water-sliding film on a substrate by forming an underlayer having a surface having a double surface roughness with a surface and applying a water repellent to at least a part of the underlayer. 22. A method for producing a highly water-slidable film by subjecting a surface of a microporous layer having a large number of micropores having an average pore diameter of 100 nm to 2 μm to a water-repellent treatment. 23. A first uneven surface having a first surface roughness, and a first uneven surface having a second surface roughness smaller than the first surface roughness.
A method of producing a highly water-slidable film by subjecting a substrate surface having a double surface roughness to the second uneven surface formed on the uneven surface of the above to a water-repellent treatment. 24. The first uneven surface having a surface roughness of 100 nm or less.
2 μm, and the second uneven surface has a surface roughness of 100 n.
24. The method of claim 23, wherein the difference is less than m. 25. The method according to claim 19, wherein a fluorine-based water repellent is applied. 26. The lubricating water film finally obtained by adjusting the state of the phase separation and / or adjusting the heat treatment step by using the coating agent according to claim 15. A method for adjusting aqueous strength and / or adjusting hardness.