JP5804548B2 - Super water- and oil-repellent antifouling translucent film, production method thereof, glass window using them, solar energy utilization device, optical device, and display device - Google Patents

Description

The present invention relates to a super-water / oil / oil / fouling and translucent film having a water droplet contact angle of 130 ° or more, a method for producing the film, a glass window using the same, a solar energy utilization device, an optical device, and a display device, and more Specifically, a highly water- and oil-repellent antifouling light-transmitting film having a highly durable and water-repellent and oil-repellent antifouling film formed thereon, a method for producing the same, a glass window using them, and solar energy The present invention relates to a utilization device, an optical device, and a display device.

In recent years, with the improvement of living standards and the enhancement of hygiene awareness, countermeasures against contamination of articles around us have been demanded. Display devices used in various information devices and operation terminals are also required to have improved antifouling properties for reasons such as improved visibility and reduced maintenance costs, particularly public health requirements for touch panel displays.

Touch panel displays can be installed in facilities such as bank ATMs, vending machines, personal digital assistants (PDAs), copiers, facsimiles, game machines, museums, department stores, etc., car navigation systems, multimedia stations (at convenience stores) Widely used in installed multifunction terminals, mobile phones, railway vehicle monitoring devices, etc. In addition to sanitary requirements, fingerprint adhesion prevention and wear resistance from the viewpoint of ensuring visibility and operability Is strongly demanded.

There are two methods for preventing contamination on the surface of the member: a method of forming a film having a small surface energy on the surface of the member and a surface treatment method of reducing the surface energy of the surface of the member itself. There are demands for a small number of technologies and manufacturing technologies that cause less environmental damage when disposing of products.

For example, Patent Document 1 discloses a technique for performing an antifouling treatment on a member surface itself using fluorine gas.

Patent Document 2 discloses a display surface material having an uneven surface formed by applying an alumina sol solution and then immersing it in warm water.

Patent Document 3 discloses a fingerprint-resistant photocurable composition that can improve fingerprint resistance on the surface of an optical display device by a very simple process such as coating.

JP-A-2005-290118 JP 2007-34027 A JP 2008-255301 A

However, the method described in Patent Document 1 has a problem that the efficiency is poor because a long time (several hours) is required for the reaction in addition to the safety problem caused by the use of toxic fluorine gas. doing. The production of the display surface material described in Patent Document 2 requires a complicated process such as immersion in warm water after the sol is applied. Although the fingerprint-resistant photocurable composition described in Patent Document 3 can form a fingerprint-resistant film by a simple operation, it has problems such as difficulty in forming a uniform film over a large area. Furthermore, it is difficult to form irregularities on the surface effective for improving water and oil repellency and antifouling properties.

The present invention has been made in view of such circumstances, and by providing complex irregularities on the surface, such as water and oil repellency and antifouling function, water droplet water separation (also referred to as water slidability), oil repellency, fingerprint resistance, etc. An object of the present invention is to provide a super water / oil / oil repellent light-transmitting film having improved anti-stain properties, a method for producing the same, a glass window using the same, a solar energy utilization device, and an optical instrument.

The first aspect of the present invention that meets the above-mentioned object is a film surface layer made of a material having translucency,
It is embedded in the film surface layer so that at least a part of the surface is exposed, and the surface of a spherical or substantially spherical fine particle is formed with a plurality of spherical or substantially hemispherical protrusions having a diameter smaller than that of the fine particle. a transparent composite fine particles having a structure, and a water- and oil-repellent antifouling film coupled formed so as to cover at least a part of the surface of the composite fine particles exposed from the film surface layer possess, the film surface The layer has a first reactive functional group, and the composite fine particle has a second reactive functional group that forms a bond by reacting with the first reactive functional group, and the composite fine particle Is bonded and fixed to the film surface layer through a bond formed by the reaction of the first and second reactive functional groups . The above section by providing a film It is intended to solve.

Complex irregularities are formed by complex fine particles having a confetti-like structure composed of substantially spherical fine particles at least partly exposed from the film surface layer and a plurality of smaller substantially hemispherical protrusions formed on the surface. A so-called fractal surface structure is obtained. Therefore, the water and oil repellency and antifouling properties can be greatly improved even when the surface has a flat surface. In addition, by forming a water / oil / oil repellent thin film on the surface of the composite fine particles, water repellency, oil repellency and antifouling properties can be improved.

In the super water / oil repellent antifouling light-transmitting film according to the first aspect of the present invention, the fine particles may have a diameter of 50 to 100 nm, and the protrusion may have a diameter of 10 to 20 nm.
Since the size of the composite fine particles is smaller than the shortest wavelength (400 nm) of visible light, the scattering and diffuse reflection of incident light is suppressed, and a super water and oil repellent and antifouling translucent film excellent in transparency and optical properties is provided. it can.

In the super water / oil repellent antifouling light-transmitting film according to the first aspect of the present invention, the fine particles and the protrusions are made of a material selected from the group consisting of glass, silica, alumina and zirconia. May be.
Since the composite fine particles are made of a material selected from the group consisting of glass, silica, alumina, and zirconia, it is excellent in transparency and can improve the durability of the surface of the super water / oil repellent / antifouling translucent film.

In this case, it is particularly preferable that the first and second reactive functional groups are both functional groups that do not undergo a dimerization reaction under the production conditions of the super water / oil / oil repellent / light-transmitting film.

In the super water / oil repellent antifouling and translucent film according to the first aspect of the present invention, the critical surface energy of the surface is ideally low, but may be 1 mN / m or more and 3 mN / m or less. preferable.
Since the critical surface energy of the surface is in the above range, all of the water repellency, oil repellency and antifouling property of the resulting super water / oil repellency / antifouling light-transmitting film can be improved.

According to a second aspect of the present invention, there is provided at least transparent composite fine particles having a confetti-like structure in which a plurality of spherical or hemispherical protrusions having a smaller diameter than the fine particles are formed on the surface of spherical or substantially spherical fine particles. A step D of embedding in a film surface layer having translucency so that a part of the film is exposed, and a step of forming a water- and oil-repellent and antifouling thin film on the surface of the composite fine particles exposed from the film surface layer It possesses the E, respectively the composite fine particles, across a first surface reactive groups to form a bond by reacting with the first surface functional groups of the fine particles of spherical or substantially spherical, and a first reactive group A first reaction liquid containing the first film compound having the first fine particle is brought into contact with the surface of the first fine particle, and the first fine particle is formed through a bond formed by a reaction between the surface functional group and the surface reactive group. Fixed to the surface of the first Step A for forming a film of the film compound, and a second surface reactive group that forms a bond by reacting with a surface functional group of a second fine particle that is spherical or substantially spherical and has a diameter smaller than that of the first fine particle. A second reaction solution containing a second film compound having both ends of the first reactive group and a second reactive group that reacts with the first reactive group to form a bond with the surface of the second microparticle. Forming a coating film of the second film compound bonded and fixed to the surface of the second fine particle through a bond formed by a reaction between the surface functional group and the surface reactive group, and The first fine particles on which the film of the first film compound is formed and the second fine particles on which the film of the second film compound is formed are brought into contact with each other, and the first reactive group and the second fine particles are brought into contact with each other. Of the first membrane compound through the bond formed. And C for preparing a confetti-like composite fine particle in which a plurality of the second fine particles on which the film of the second film compound is formed are bonded and fixed to the surface of the first fine particle on which the film is formed. The above-mentioned problems are solved by providing a method for producing a super water- and oil-repellent antifouling and light-transmitting film characterized by being produced by the method .

By means of the composite fine particles having a saccharosaccharide-like structure composed of substantially spherical fine particles at least partially exposed from the film surface layer and a plurality of substantially hemispherical protrusions smaller than the first protrusions, A surface structure of a so-called fractal structure with complex irregularities is provided. Therefore, water repellency, oil repellency and antifouling properties can be improved as compared with a film surface layer in which only a flat film surface layer and spherical fine particles are bonded and fixed to the surface. Further, in Step E, the water repellency, oil repellency and antifouling property can be further improved by forming a water / oil repellency / antifouling thin film on the surface of the composite fine particles.

In C from A as engineering, the first thing that the coating of the second film compound on the surface of the fine particles to a plurality of fixed coupling said second particles forming the first coating formed, inexpensive spherical It is possible to easily prepare confetti-like composite fine particles using the fine particles.

In the method for producing a super water / oil repellent antifouling and translucent film according to the second aspect of the present invention, the diameter of the first fine particles is 50 to 100 nm, and the diameter of the second fine particles is 10 to 10 nm. It is preferably 20 nm.
Since the size of the composite fine particles is smaller than the shortest wavelength (400 nm) of visible light, the scattering and diffuse reflection of incident light is suppressed, and a super water and oil repellent and antifouling translucent film excellent in transparency and optical properties is provided. it can.

In the method for producing a super water / oil repellent / antifouling and translucent film according to the second aspect of the present invention, the composite fine particles prepared in the step C are further heat-treated to obtain a surface of the first fine particles. The second fine particles may be fused.

In the method for producing a super water / oil repellent antifouling and translucent film according to the second aspect of the present invention, the first fine particles on which the film of the first film compound is formed after the step C The second fine particles on which the coating film of the second film compound that has not been bonded and fixed to the surface may be washed away.

In the method for producing a super water / oil repellent antifouling and translucent film according to the second aspect of the present invention, in the step E, any one of functional groups present on the surface of the film surface layer and the composite fine particles. Alternatively, the film in which the composite fine particles are bonded and fixed with a water / oil repellent / antifouling treatment liquid containing a third film compound having a third surface reactive group and a fluorocarbon group that react with a plurality to form a bond. The surface is brought into contact with the surface of the surface layer, and the surface is formed through a bond formed by a reaction between one or more of the functional groups present on the surface of the film surface layer and the composite fine particles and the third surface reactive group. You may form the film of the said 3rd film | membrane compound couple | bonded and fixed to.
The water / oil repellent / antifouling thin film is bonded and fixed to the surface of the composite fine particle through a bond formed by the reaction between the surface functional group and the surface reactive group, thereby improving the durability of the water / oil repellent / antifouling thin film. Can be improved.

In this case, the first to third surface reactive groups are alkoxysilyl groups, the first and second reaction liquids, and the water / oil repellent / antifouling treatment liquid are:
(1) one or more compounds selected from the group consisting of carboxylic acid metal salts, carboxylic acid ester metal salts, carboxylic acid metal salt polymers, carboxylic acid metal salt chelates, titanate esters and titanate ester chelates, and / or Alternatively, (2) one or more compounds selected from the group consisting of ketimine compounds, organic acids, aldimine compounds, enamine compounds, oxazolidine compounds, and aminoalkylalkoxysilane compounds may be included as a condensation catalyst.
By using an alkoxysilyl group as a surface reactive group, it is possible to prevent the formation of harmful by-products such as hydrogen halide during the reaction, and the reaction solution contains a condensation catalyst, so that it is water and oil repellent and antifouling. The processing time required for forming a conductive thin film can be shortened.

Further, after the step E, the excess water / oil repellent / antifouling treatment solution may be removed by washing.
By washing and removing excess reaction liquid, the water- and oil-repellent and antifouling thin film can be made into a monomolecular film, thus impairing the transparency of the manufactured super water and oil repellent and antifouling translucent film. There is no.

According to a third aspect of the present invention, spherical or substantially spherical fine particles or spherical or substantially spherical particles are contained in a solvent containing a binder precursor that generates a binder that can be bonded to the surface of the film substrate by evaporation of the solvent and subsequent heating. A dispersion liquid in which slab-like composite fine particles, in which a plurality of spherical or hemispherical projections having a smaller diameter than the fine particles are bonded and fixed, is applied to the surface of the spherical fine particles is applied to the surface of the film substrate, and then the solvent is evaporated. And a step a for binding and fixing the fine particles or the composite fine particles to the surface of the film surface layer via the binder precursor,
The fine particles or the composite fine particles and / or the fine particles adhered to or bonded to the surface of the film substrate through the binder precursor by etching a part of the surface of the binder generated on the surface of the film substrate. Or a step b of forming a plurality of spherical or substantially spherical protrusions smaller than the fine particles on the surface of the composite fine particles and / or the film substrate;
The film base material having the fine particles or the composite fine particles attached or bonded to the surface via the binder precursor is heated, and the fine particles on which the protrusions are formed via the generated binder are formed on the film base material. A step c for bonding and fixing to the surface;
Wherein the microparticles bound and fixed surface of the film substrate possess a step d to form a water-repellent oil-repellent antifouling film, the film substrate is transparent both the particles and the binder, the To provide a method for producing a super water / oil repellent / antifouling and translucent film characterized in that the height of the confetti formed on the surface of the film substrate in step c is 30 to 300 nm. The above-mentioned problem is solved.

In the method for producing a super water / oil repellent antifouling and translucent film according to the third aspect of the present invention, the fine particles preferably have a diameter of 50 to 100 nm.
Since the size of the composite fine particles is smaller than the shortest wavelength (400 nm) of visible light, the scattering and diffuse reflection of incident light is suppressed, and a super water and oil repellent and antifouling translucent film excellent in transparency and optical properties is provided. it can.

In the method for producing a super water / oil repellent antifouling translucent film according to the third aspect of the present invention, chemical etching or physical etching may be used as a method of etching a part of the surface of the binder.

In the method for producing a super water / oil repellent antifouling translucent film according to the third aspect of the present invention, the heating temperature in the step c is preferably lower than the softening point of the film substrate.

In the method for producing a super water / oil repellent / antifouling and translucent film according to the third aspect of the present invention, in the step d, any one of functional groups present on the surfaces of the film substrate and the composite fine particles. Alternatively, a water / oil repellent / antifouling treatment liquid containing a film compound having a surface reactive group and a fluorocarbon group that reacts with a plurality to form a bond is brought into contact with the surface of the film substrate to which the composite fine particles are bonded and fixed. And the membrane compound bonded and fixed to the surface through a bond formed by the reaction of any one or more of the functional groups present on the surface of the film substrate and the composite fine particles with the surface reactive group A film may be formed.
The water / oil repellent / antifouling thin film is bonded and fixed to the surface of the composite fine particle through a bond formed by the reaction between the surface functional group and the surface reactive group, thereby improving the durability of the water / oil repellent / antifouling thin film Can be improved.

In the method for producing a super water / oil repellent / antifouling light-transmitting film according to the third aspect of the present invention, the surface reactive group is an alkoxysilyl group, and the water / oil repellent / antifouling treatment liquid comprises:
(1) one or more compounds selected from the group consisting of carboxylic acid metal salts, carboxylic acid ester metal salts, carboxylic acid metal salt polymers, carboxylic acid metal salt chelates, titanate esters and titanate ester chelates, and / or Alternatively, (2) one or more compounds selected from the group consisting of ketimine compounds, organic acids, aldimine compounds, enamine compounds, oxazolidine compounds, and aminoalkylalkoxysilane compounds may be included as a condensation catalyst.
By using an alkoxysilyl group as a surface reactive group, it is possible to prevent the formation of harmful by-products such as hydrogen halide during the reaction, and the reaction solution contains a condensation catalyst, so that it is water and oil repellent and antifouling. The processing time required for forming a conductive thin film can be shortened.

Further, after the step d, the excess water / oil repellent / antifouling treatment liquid may be removed by washing.
By washing and removing excess reaction liquid, the water- and oil-repellent and antifouling thin film can be made into a monomolecular film, thus impairing the transparency of the manufactured super water and oil repellent and antifouling translucent film. There is no.

In the method for producing a super water / oil repellent antifouling and translucent film according to the third aspect of the present invention, the step c may be performed before the step b.

According to a fourth aspect of the present invention, there is provided a glass window having a super water / oil repellent antifouling and translucent film according to the first aspect of the present invention on its surface, thereby solving the above-mentioned problems. .
In addition to water repellency, oil repellency and antifouling properties, a glass window having excellent transparency and durability can be provided.

According to a fifth aspect of the present invention, there is provided a solar energy utilization apparatus in which the super water / oil / oil repellent and light-transmitting film according to the first aspect of the present invention is installed on the surface of the face plate. It is a solution.
In addition to water repellency, oil repellency, and antifouling properties, it is possible to provide a solar energy utilization device that is excellent in durability and weather resistance, and that is excellent in light energy utilization efficiency because scattering and diffuse reflection of incident light are suppressed.

According to a sixth aspect of the present invention, there is provided an optical apparatus having the super water / oil repellent antifouling and translucent film according to the first aspect of the present invention to solve the above-mentioned problems.
In addition to water repellency, oil repellency, and antifouling properties, it is excellent in durability and weather resistance, and since scattering and irregular reflection of incident light are suppressed, an optical device excellent in transparency and optical characteristics can be provided.

According to a seventh aspect of the present invention, there is provided a display device having the super water / oil repellent antifouling light-transmitting film according to the first aspect of the present invention.
In addition to water repellency, oil repellency and antifouling properties, it also has excellent durability and weather resistance, and since it suppresses scattering and irregular reflection of incident light, it has excellent transparency and optical properties, and also has excellent fingerprint resistance. A display device that can provide the device can be provided.

According to the present invention, in addition to the water / oil repellent / antifouling function, super water / oil repellent with improved durability, such as abrasion resistance and weather resistance, water-drop separation (also referred to as water slidability), oil repellency and antifouling properties. An oil antifouling translucent film and a method for producing the same are provided. Further, according to the present invention, in addition to water repellency, oil repellency and antifouling properties, glass windows with excellent transparency and durability, water repellency, oil repellency and antifouling properties, weather resistance and utilization of light energy A solar energy utilization device having excellent efficiency and an optical apparatus having excellent durability, transparency, and optical characteristics in addition to water repellency, oil repellency and antifouling properties are provided. Furthermore, a display device having excellent fingerprint resistance can be provided.
In the method for producing a super water / oil repellent antifouling light-transmitting film of the present invention, after forming the confetti-like composite fine particles, it is embedded in the film surface layer so that a part of the fine particles is exposed. Complex indentations are brought about, the water droplet contact angle is 145 degrees or more, and the water and oil repellency and antifouling properties can be greatly improved as compared to about 110 degrees when flat.

It is explanatory drawing which demonstrated typically the cross-section of the super water / oil repellent antifouling translucent film which concerns on the 1st Embodiment of this invention. It is explanatory drawing of the process of manufacturing a composite microparticle in the manufacturing method of the super water-repellent oil-repellent antifouling translucent film. In the method for producing a wear-resistant super water- and oil-repellent antifouling translucent film according to the second embodiment of the present invention, a plurality of fine particles bonded and fixed to the surface of the film substrate via a binder are provided. It is explanatory drawing of the process of forming the spherical or substantially spherical protrusion. 2 is a scanning electron microscope (SEM) photograph of the surface of a wear-resistant super water / oil / oil repellent and light-transmitting film produced in Example 1. FIG.

Next, embodiments of the present invention will be described with reference to the accompanying drawings for understanding of the present invention. 1 to 3 are merely schematic explanatory views. The size of the compound that forms the film surface layer, composite fine particles or fine particles, and the water / oil repellent / antifouling thin film is not necessarily the ratio of the actual size. Not reflected.
As shown in FIG. 1, the super water / oil repellent / antifouling translucent film 10 according to the first embodiment of the present invention includes a film surface layer 14 made of a translucent material and at least a part thereof. Embedded in the film surface layer 14 so as to be exposed on the surface, and has a confetti-like structure in which a plurality of spherical or substantially hemispherical protrusions 13 having a smaller diameter are formed on the surface of spherical or substantially spherical fine particles. A transparent fused composite fine particle 11a (an example of a composite fine particle), and a water / oil / oil repellent antifouling thin film 15a formed so as to cover at least part of the surface of the composite fine particle 11 exposed from the film surface layer 14; Have

The super water- and oil-repellent antifouling and translucent film 10 has a transparent structure having a confetti structure in which a plurality of spherical or hemispherical protrusions having a smaller diameter than the fine particles are formed on the surface of spherical or substantially spherical fine particles. Embedded in the film surface layer having translucency so that at least a part of the composite fine particle 11 is exposed on the surface, and the surface of the composite fine particle 11 exposed from the film surface layer 14 is water- and oil-repellent and oil-proof. And a step E of forming the dirty thin film 15a.
Hereinafter, the processes D and E will be described in more detail.

(1) Process D
As the film surface layer 14 constituting the super water / oil repellent / antifouling translucent film 10, any material, shape and size can be used without particular limitation as long as the surface layer of the translucent film can be formed. . The film surface layer 14 may be integrated with the film base material, and is a film such as a hard coat layer provided on the surface of the film base material for the purpose of improving wear resistance, scratch resistance, antiglare property, etc. It may be a surface layer separate from the substrate. As the material of the film surface layer 14, acrylic resin, oxetane resin, silicone resin, polyurethane resin, fluorine resin, polyethylene terephthalate (PET), triacetyl cellulose (TAC), polyimide (PI), any two of these Examples thereof include organic polymers such as the above copolymers, inorganic polymers such as silica, and composites or laminates thereof.

The fused composite fine particle 11a has a confetti-like shape in which a plurality of spherical or hemispherical projections 13 having a smaller diameter are fused on the surface of a spherical or substantially spherical fine particle 12, and includes a projection. The diameter of the non-spherical part is 50 nm to 5 mm, preferably 50 nm to 400 nm, more preferably 50 to 100 nm. In particular, for the production of a super water- and oil-repellent antifouling translucent film 10 that requires transparency for use in glass windows, solar energy utilization devices, optical devices, touch panels and other display devices, etc. In order to suppress a decrease in transparency due to light scattering or irregular reflection, the diameter of the spherical portion not including the protrusions of the fused composite fine particles 11a needs to be 400 nm or less, which is shorter than the wavelength of visible light, and is the most preferable diameter. The range is 50-100 nm as described above.

The diameter of the protrusion is 1/100 or more and 1/5 or less of the diameter of the spherical part not including the protrusion of the fused composite fine particle 11a, and is 1 nm to 50 μm, preferably 5 nm to 80 nm, more preferably 10 to 20 nm.

There are no particular restrictions on the material of the fused composite fine particles 11a, and any material such as soda-lime glass, crystal glass, quartz glass, borosilicate glass, glass ceramics, silica, alumina, zirconia, etc. can be used. An organic material such as acrylic glass (plexiglass) made of methyl acid can also be used. In particular, when fine particles made of a hard inorganic oxide such as silica, alumina, or zirconia are used, the surface hardness and wear resistance of the resulting super water / oil / oil repellent and translucent film 10 can be improved.

As long as the fused composite fine particles 11a have the shape and size as described above, the production method is not particularly limited and those produced using any method can be used. When the method including the steps A to C is used, a controlled particle can be easily prepared using inexpensive spherical fine particles.

The fusion composite fine particles 11a are embedded in the film surface layer 14 by, for example, (1) spraying and press-fitting the fusion composite fine particles 11a onto the film surface layer 14 softened by heating. (2) The film surface layer 14 The liquid precursor and the fused composite fine particles 11a can be applied to a film substrate, and then the precursor is reacted to form the film surface layer 14. Moreover, you may use photocurable resin and an adhesive agent (an epoxy adhesive, a cyanoacrylate adhesive) as a binder. Since all of these processes can be performed by the conventional roll-to-roll method, existing production facilities can be used and it is easy to cope with an increase in area.

Reactive functional group (an example of a first reactive functional group) possessed by the film surface layer 14 or its precursor, and a functional group on the surface of the composite fine particle 11 (an example of a second reactive functional group) React to form a bond, and the embedded composite fine particle 11 is bonded and fixed to the film surface layer 14 through the bond. The wear resistance and scratch resistance of the conductive film 10 can be improved. When an inorganic oxide such as silica or alumina is used as the composite fine particle 11, since it has a hydroxyl group as a surface group, the film surface layer 14 having a functional group that reacts therewith or a precursor thereof may be selected. Specific examples thereof include silica precursors such as alkoxysilanes, silicone resin precursors, and the like.

Or the alkoxysilane compound which has the reactive functional group which the film surface layer 14 or its precursor has at one end is made to react with the composite fine particles 11 under the same conditions as in Steps A, B and E described later, and the composite fine particles 11 The reactive functional group may be introduced on the surface.

In these cases, the surface functional group of the composite fine particle 11 or the reactive functional group introduced into the surface by the reaction with the alkoxysilane compound as described above forms a bond in a state where the composite fine particle is aggregated, In order to avoid the uneven distribution of the composite fine particles 11 in the film surface layer 14, it is preferable that the dimerization reaction does not occur under the manufacturing conditions of the super water / oil repellent / antifouling and translucent film 10.

In this way, the fused composite fine particles 11a embedded in the film surface layer 14 so that a part of the surface is exposed to the surface are spherical or hemispherical having a smaller diameter on the surface of the spherical or substantially spherical fine particles 12. The plurality of second protrusions 13 has a fused sugar-like shape, and the height thereof is 50 nm to 5 mm, preferably 50 nm to 400 nm, more preferably 50 to 100 nm. In particular, for the production of a super water- and oil-repellent antifouling translucent film 10 that requires transparency for use in glass windows, solar energy utilization devices, optical devices, touch panels and other display devices, etc. In order to suppress a decrease in transparency due to light scattering or irregular reflection, the height of the fused composite fine particles 11a needs to be 400 nm or less, which is shorter than the wavelength of visible light.

The diameter of the second protrusion 13 is 1/100 or more and 1/5 or less of the diameter of the fine particles 12, and is 1 nm to 50 μm, preferably 5 nm to 80 nm, more preferably 10 to 20 nm.

Process E
A water- and oil-repellent and antifouling thin film bonded and fixed to the surface of the composite fine particle 11 exposed from the film surface layer 14 through a bond formed by a reaction between a surface functional group and a surface reactive group (not shown). The reaction liquid used to produce the super water / oil repellent / antifouling and translucent film 10 is an alkoxysilane compound containing a fluorocarbon group (a film having a surface reactive group and a fluorocarbon group). An example of the compound 15, a condensation catalyst for promoting the condensation reaction between the hydroxyl group (an example of the surface functional group) on the surface of the composite fine particle 11 exposed from the film surface layer 14 and the alkoxysilyl group, and a non-aqueous organic material It is prepared by mixing with a solvent.

Examples of the alkoxysilane compound containing a fluorocarbon group include alkoxysilane compounds represented by the following general formula (I).

_{(I) CF 3 (CF 2} ) n -Y-Z- (CH 2) m -Si (OR) 3

In the above formula, m represents an integer of 0 to 20, n represents an integer of 0 to 9, and R represents an alkyl group having 1 to 4 carbon atoms.
Y represents (CH ₂ ) _k (k represents an integer of 1 to 3) and a single bond, and Z represents O (ether oxygen), COO, Si (CH ₃ ) ₂ , and a single bond. Represents one of the bonds.

Examples of the alkoxysilane compound containing a fluorocarbon group represented by the formula (I) include compounds shown in the following (1) to (12).

(1) CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃
(2) CF ₃ (CH ₂ ) ₃ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃
(3) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OCH ₃ ) ₃
(4) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OCH ₃ ) ₃
(5) CF ₃ COO (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃
(6) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
(7) CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₃
(8) CF ₃ (CH ₂ ) ₃ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₃
(9) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OC ₂ H ₅ ) ₃
(10) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OC ₂ H ₅ ) ₃
(11) CF ₃ COO (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₃
(12) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃

As the condensation catalyst, metal salts such as carboxylic acid metal salts, carboxylic acid ester metal salts, carboxylic acid metal salt polymers, carboxylic acid metal salt chelates, titanate esters and titanate ester chelates can be used.
The addition amount of the condensation catalyst is preferably 0.2 to 5% by mass of the alkoxysilane compound, and more preferably 0.5 to 1% by mass.

Specific examples of carboxylic acid metal salts include stannous acetate, dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, dioctyltin diacetate, stannous dioctanoate, naphthenic acid Lead, cobalt naphthenate, and iron 2-ethylhexenoate.

Specific examples of the carboxylic acid ester metal salt include dioctyltin bisoctylthioglycolate ester salt and dioctyltin maleate ester salt.
Specific examples of the carboxylic acid metal salt polymer include dibutyltin maleate polymer and dimethyltin mercaptopropionate polymer.
Specific examples of the carboxylic acid metal salt chelate include dibutyltin bisacetylacetate and dioctyltin bisacetyllaurate.

Specific examples of the titanate ester include tetrabutyl titanate and tetranonyl titanate.
Specific examples of titanate chelates include bis (acetylacetonyl) dipropyl titanate.

When the reaction solution is applied to the surface of the composite fine particle 11 exposed from the film surface layer 14 and reacted in air at room temperature, the alkoxysilyl group and the hydroxyl group on the surface of the composite fine particle 11 exposed from the film surface layer 14 are condensed. A reaction is caused to generate a water / oil / oil repellent antifouling thin film 15a containing a fluorocarbon group having a structure as shown in Chemical Formula 1 below. The three single bonds extending from the oxygen atoms are bonded to the surface of the composite fine particles 11 exposed from the film surface layer 14 or the silicon (Si) atoms of the adjacent silane compound, at least one of which is the film surface layer. 1 is bonded to silicon atoms on the surface.

Since the alkoxysilyl group decomposes in the presence of moisture, the reaction is preferably performed in air with a relative humidity of 45% or less. The condensation reaction is hindered by oils and fats and moisture adhering to the surface of the composite fine particles 11 exposed from the film surface layer 14, so that the composite fine particles 11 exposed from the film surface layer 14 are thoroughly washed and dried. It is preferable to remove these impurities in advance.
When any of the above metal salts is used as the condensation catalyst, the time required for completion of the condensation reaction is about 2 hours.

When one or more compounds selected from the group consisting of ketimine compounds, organic acids, aldimine compounds, enamine compounds, oxazolidine compounds, and aminoalkylalkoxysilane compounds are used as the condensation catalyst instead of the above metal salts, Time can be shortened to about 1/2 to 2/3.

Alternatively, when these compounds are used as a co-catalyst and mixed with the above-described metal salt (mass ratio 1: 9 to 9: 1 can be used, preferably around 1: 1), the reaction time is further shortened. it can.

For example, when H3 from Japan Epoxy Resin Co., which is a ketimine compound, is used as the condensation catalyst instead of dibutyltin oxide and the other conditions are the same, the reaction time can be reduced to about 1 hour.

Furthermore, when the reactive film surface layer 4 is produced using a mixture of H3 and dibutyltin bisacetylacetonate (mixing ratio is 1: 1) of Japan Epoxy Resin Co., Ltd. as the condensation catalyst, under the same other conditions. The reaction time can be shortened to about 20 minutes.

The ketimine compound that can be used here is not particularly limited, and examples thereof include 2,5,8-triaza-1,8-nonadiene, 3,11-dimethyl-4,7,10-triaza- 3,10-tridecadiene, 2,10-dimethyl-3,6,9-triaza-2,9-undecadiene, 2,4,12,14-tetramethyl-5,8,11-triaza-4,11-penta Decadiene, 2,4,15,17-tetramethyl-5,8,11,14-tetraaza-4,14-octadecadiene, 2,4,20,22-tetramethyl-5,12,19-triaza -4,19-trieicosadiene and the like.

The organic acid that can be used is not particularly limited, and examples thereof include formic acid, acetic acid, propionic acid, butyric acid, and malonic acid.

For the preparation of the reaction solution, an organic chlorine solvent, a hydrocarbon solvent, a fluorocarbon solvent, a silicone solvent, and a mixed solvent thereof can be used. In order to prevent hydrolysis of the alkoxysilane compound, it is preferable to remove water from the desiccant or the solvent used by distillation. Moreover, it is preferable that the boiling point of a solvent is 50-250 degreeC.

As the specifically usable solvent, any solvent can be used as long as it does not dissolve or swell the film substrate or the film surface layer 14, but non-aqueous petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzine, Examples include isoparaffin, normal paraffin, decalin, industrial gasoline, nonane, decane, kerosene, dimethyl silicone, phenyl silicone, alkyl-modified silicone, polyether silicone, and dimethylformamide.
Furthermore, alcohol solvents such as methanol, ethanol, propanol, or a mixture thereof can also be used.

Fluorocarbon solvents that can be used include fluorocarbon solvents, Fluorinert (manufactured by 3M, USA), Afludo (manufactured by Asahi Glass Co., Ltd.), and the like. In addition, these may be used individually by 1 type and may mix 2 or more types as long as it mixes well. Furthermore, an organic chlorine solvent such as dichloromethane or chloroform may be added.

The preferable density | concentration of the alkoxysilane compound in a reaction liquid is 0.5-3 mass%.

After the reaction, the substrate is washed with a solvent to remove excess alkoxysilane compound and condensation catalyst remaining on the surface as unreacted substances, and then the surface is covered with a water / oil / oil / oil repellent thin film 15a. The translucent film 10 is obtained.

As the cleaning solvent, any solvent that can dissolve the alkoxysilane compound and does not dissolve or swell the film substrate or the film surface layer 14 can be used, but it is inexpensive, has high solubility, and is easily removed by air drying. Preferred are dichloromethane, chloroform, N-methylpyrrolidone and the like.

After the reaction, if the excess reaction solution is left in the air without being washed away with a solvent, a part of the alkoxysilane compound remaining on the surface is hydrolyzed by moisture in the air, and the generated silanol group becomes an alkoxysilyl group. Causes a condensation reaction. As a result, an ultrathin polymer film made of polysiloxane is formed on the surface of the super water / oil repellent antifouling and translucent film 10. This polymer film is not fixed to the surface of the super water / oil / oil repellent / stain-resistant translucent film 10 by covalent bond, but has water / oil / oil / oil / stain resistance because it has a fluorocarbon group. ing. Therefore, it can be used as the super water / oil repellent antifouling translucent film 10 even in this state except for the point that the durability is somewhat inferior.

Although the case where an alkoxysilane compound is used has been described in this embodiment mode, a halosilane compound having a fluorocarbon group may be used. When a halosilane compound is used, a condensation catalyst and a cocatalyst are not required, an alcohol solvent cannot be used, and it is more susceptible to hydrolysis than an alkoxysilane compound. %), The reaction liquid can be prepared and reacted with the composite fine particles 11 exposed from the film surface layer 14 in the same manner as the alkoxysilane compound.

Since the film thickness of the monomolecular film-like water- and oil-repellent and antifouling thin film 15a is about 1 nm at most, the unevenness of about 5 to 50 nm formed on the surface of the composite fine particles 11 exposed from the film surface layer 14 is almost lost. It will not be. In addition, the uneven surface effect (the so-called “lotus leaf effect”) can reduce the apparent surface energy of the super water / oil / oil repellent and light-transmitting film 10, and the water droplet contact angle is 140 ° or more (present) In the embodiment, it is about 150 °), and super water repellency can be realized.

Moreover, as a halosilane compound containing the fluorocarbon group which can be used in the process E, the compound shown to following (21)-(26) is mentioned. Moreover, the isocyanate silane compound shown to following (27)-(32) can also be used.

(21) CF ₃ CH ₂ O (CH ₂ ) ₁₅ SiCl ₃
(22) CF ₃ (CH ₂ ) ₃ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ SiCl ₃
(23) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ SiCl ₃
(24) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ SiCl ₃
(25) CF ₃ COO (CH ₂ ) ₁₅ SiCl ₃
(26) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ SiCl ₃
(27) CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (NCO) ₃
(28) CF ₃ (CH ₂ ) ₃ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si (NCO) ₃
(29) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (NCO) ₃
(30) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (NCO) ₃
(31) CF ₃ COO (CH ₂ ) ₁₅ Si (NCO) ₃
(32) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (NCO) ₃

The water / oil repellent / antifouling thin film 15 a may be formed on the surface of the film surface layer 14. When there is a surface functional group capable of reacting with an alkoxysilane compound containing a fluorocarbon group in the film surface layer 14, it can react with the above-mentioned alkoxysilane compound. Also, the water / oil repellent antifouling thin film 15a can be formed. Even if there is no surface functional group capable of reacting with an alkoxysilane compound containing a fluorocarbon group on the film surface layer 14, the alkoxysilane compound and the surface of the film surface layer 14 are pretreated by corona treatment or the like. Surface functional groups such as reactive hydroxyl groups can be introduced.

Preparation of Fusion Composite Fine Particles The fusion composite fine particles 11a include a first surface reactive group that reacts with a surface functional group of the spherical or substantially spherical first fine particle 21 to form a bond, and a first reactive group. A first reaction liquid containing a first film compound at each end is brought into contact with the surface of the first fine particle, and the first fine particle is formed through a bond formed by a reaction between a surface functional group and a surface reactive group. Reacting with the surface functional groups of the second microparticles 22 which are spherical or substantially spherical and have a diameter smaller than that of the first microparticles 21; A second reaction solution containing a second film compound having both a second surface reactive group that forms a bond and a second reactive group that reacts with the first reactive group to form a bond at both ends. Is brought into contact with the surface of the second fine particle 22, and a surface functional group and a surface reactive group A step B of forming a film of the second film compound bonded and fixed to the surface of the second fine particle 22 through a bond formed by the reaction; and a first fine particle on which the film of the first film compound is formed 21 is brought into contact with the second fine particles 22 on which the film of the second film compound is formed, the first reactive group and the second reactive group are reacted, and the first reactive group is formed via the formed bond. After preparing the confetti-like composite fine particles 11 in which a plurality of the second fine particles 22 with the second film compound film formed thereon are bonded and fixed to the surface of the first fine particles 21 with the film compound film formed thereon, You may prepare by the method which has the process C (refer FIG. 2) which prepares the fusion | melting composite fine particle 11a which heated and fuse | melted the 1st fine particle 21 and the 2nd fine particle 22. FIG.
Hereinafter, each process will be described in more detail.

Process A
The shape of the first fine particles 21 is not particularly limited, but is preferably spherical or substantially spherical. The size of the first fine particles 21 is 50 nm to 5 mm, preferably 50 nm to 400 nm, more preferably 50 to 200 nm. In particular, for the production of a super water- and oil-repellent and antifouling translucent film 10 that requires transparency for use in glass windows, solar energy utilization devices, optical devices, display devices, etc., scattering of incident light In order to suppress a decrease in transparency due to or irregular reflection, the size of the first fine particles 21 needs to be 400 nm or shorter, which is shorter than the wavelength of visible light. The material of the first fine particles 21 is not particularly limited, and any material such as soda lime glass, crystal glass, quartz glass, borosilicate glass, glass ceramics, silica, alumina, zirconia, and the like can be used. An organic material such as acrylic glass (plexiglass) made of methyl methacrylate or the like can also be used. In particular, when fine particles made of a hard inorganic oxide such as silica, alumina, or zirconia are used, the surface hardness and wear resistance of the resulting super water / oil / oil repellent and translucent film 10 can be improved.

A non-aqueous system comprising an alkoxysilane compound (first film compound) containing a first reactive group, a condensation catalyst for promoting a condensation reaction between the alkoxysilyl group and the surface functional group (hydroxyl group) of the composite fine particle 11, A film of the first film compound is formed on the surface of the first fine particle 21 by bringing the first fine particle 21 into contact with the alkoxysilane compound in a reaction solution containing an organic solvent.

As a 1st reactive group, the epoxy group which opposes nucleophiles, such as an amino group, with a heat | fever is mentioned, for example. The alkoxysilane compound containing an epoxy group has a functional group containing an epoxy group (oxirane ring) and an alkoxysilyl group at both ends of the linear alkylene group, and is represented by the following general formula (Formula 2). An alkoxysilane compound is preferable.

In the above formula, E represents a functional group containing an epoxy group, m represents an integer of 3 to 20, and R represents an alkyl group having 1 to 4 carbon atoms.

As an example of the alkoxysilane compound which has an epoxy group, the compound shown to following (31)-(42) is mentioned.

_{(31) (CH 2 OCH)} CH 2 O (CH 2) 3 Si (OCH 3) 3
_{(32) (CH 2 OCH)} CH 2 O (CH 2) 7 Si (OCH 3) 3
(33) (CH ₂ OCH) CH ₂ O (CH ₂ ) ₁₁ Si (OCH ₃ ) _{3
(34) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 2 Si (OCH 3) 3
_{(35) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 4 Si (OCH 3) 3
_{(36) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 6 Si (OCH 3) 3
_{(37) (CH 2 OCH)} CH 2 O (CH 2) 3 Si (OC 2 H 5) 3
_{(38) (CH 2 OCH)} CH 2 O (CH 2) 7 Si (OC 2 H 5) 3
_{(39) (CH 2 OCH)} CH 2 O (CH 2) 11 Si (OC 2 H 5) 3
_{(40) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 2 Si (OC 2 H 5) 3
_{(41) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 4 Si (OC 2 H 5) 3
_{(42) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 6 Si (OC 2 H 5) 3

Here, the (CH ₂ OCH) CH ₂ O— group represents a functional group (glycidyloxy group) represented by Chemical Formula 3, and the (CH ₂ CHOCH (CH ₂ ) ₂ ) CH— group represented by Chemical Formula 4 Represents a functional group (3,4-epoxycyclohexyl group).

As the first film compound, an alkoxysilane compound having an amino group and an alkoxysilyl group at both ends of a linear alkylene group and represented by the following general formula (Formula 5) may be used.

In the above formula, m represents an integer of 3 to 20, and R represents an alkyl group having 1 to 4 carbon atoms. The epoxy group may be protected with a protecting group in order to avoid side reactions with the alkoxysilyl group. The protecting group is preferably one that can be easily removed by hydrolysis or the like, and examples thereof include a ketimine derivative produced by the reaction between a ketone and an amino group.
The amino group may be a secondary amine other than the primary amine shown in Chemical Formula 5, and an alkoxysilane compound containing a functional group having an imino group such as a pyrrole group or an imidazole group may be used instead of the amino group. Can do.
In this case, examples of the alkoxysilane compound having an amino group that can be used include the compounds shown in the following (51) to (58).

(51) H ₂ N (CH ₂ ) ₃ Si (OCH ₃ ) ₃
(52) H ₂ N (CH ₂ ) ₅ Si (OCH ₃ ) ₃
(53) H ₂ N (CH ₂ ) ₇ Si (OCH ₃ ) ₃
(54) H ₂ N (CH ₂ ) ₉ Si (OCH ₃ ) ₃
(55) H ₂ N (CH ₂ ) ₅ Si (OC ₂ H ₅ ) ₃
(56) H ₂ N (CH ₂ ) ₅ Si (OC ₂ H ₅ ) ₃
(57) H ₂ N (CH ₂ ) ₇ Si (OC ₂ H ₅ ) ₃
(58) H ₂ N (CH ₂ ) ₉ Si (OC ₂ H ₅ ) ₃

The condensation catalyst, solvent, and reaction conditions that can be used for the preparation of the reaction solution are the same as in step E, and thus detailed description thereof is omitted. However, when the first reactive group is an amino group, a compound containing a tin (Sn) salt reacts with the amino group contained in the alkoxysilane derivative to generate a precipitate, and thus cannot be used as a condensation catalyst.

Process B
Although there is no restriction | limiting in particular about the shape of the 2nd microparticle 22, It is preferable that it is spherical or substantially spherical. The size of the second fine particles 22 is 1/100 or more and 1/5 or less of the diameter of the composite fine particles 11, and is 1 nm to 50 μm, preferably 5 nm to 80 nm, more preferably 5 to 50 nm. In particular, for the production of a super water- and oil-repellent antifouling light-transmitting film 10 that requires transparency for use in glass windows, solar energy utilization devices, optical equipment, etc., it is possible to use incident light scattering or irregular reflection. In order to suppress the decrease in transparency, the size of the second fine particles 22 needs to be 400 nm or less, which is shorter than the wavelength of visible light, and 1/100 or more and 1/5 or less of the diameter of the composite fine particles 11. The material of the second fine particles 13 is not particularly limited, and any material such as soda lime glass, crystal glass, quartz glass, borosilicate glass, glass ceramics, silica, alumina, zirconia, and the like can be used. An organic material such as acrylic glass (plexiglass) made of methyl methacrylate or the like can also be used. In particular, when fine particles made of a hard inorganic oxide such as silica, alumina, or zirconia are used, the surface hardness and wear resistance of the resulting super water / oil / oil repellent and translucent film 10 can be improved.

As the second reactive group, any functional group that reacts with the first reactive group to form a bond can be used. For example, when the first reactive group is an epoxy group, an amino group is used. When the first reactive group is an amino group, an epoxy group can be used. Since the membrane compound that can be used, the condensation catalyst and solvent used for the preparation of the reaction liquid, and the reaction conditions are the same as those described above, detailed description thereof is omitted.

Process C
Next, the first fine particles 21 on which the first film compound film is formed and the second fine particles 22 on which the second film compound film is formed are brought into contact with each other, and the first reactive group and the second reaction are brought into contact with each other. A plurality of second fine particles 22 in which a film of the second film compound is formed on the surface of the first fine particles 21 in which the film of the first film compound is formed through a bond formed by reacting with a group. After preparing the gold flat sugar-like composite fine particles 11 to which the first and second fine particles 21 and 22 are fused, the fused composite fine particles 11a are prepared (see FIG. 2).

The heating temperature is preferably 50 ° C. or higher. When the heating temperature is less than 50 ° C., it takes a long time for the crosslinking reaction to proceed, and the production efficiency decreases. When the heating time exceeds the melting points of the first fine particles and the second fine particles 22, the composite fine particles 11 having a desired shape cannot be obtained.

The bond used for forming the bond between the first and second film compounds may be any of a covalent bond, an ionic bond, a coordinate bond, and a bond due to intermolecular force, but energy such as heating or light. Covalent bonds formed by irradiation with rays are preferred.
As a specific example of the covalent bond formed by heating, in addition to the N—CH ₂ CH (OH) bond formed by a reaction between an epoxy group and an amino group or an imino group, it is formed by a reaction between an isocyanate group and an amino group. NH-CONH bond may be used. Specific examples of the covalent bond formed by light irradiation include a covalent bond formed by a photodimerization reaction of a cinnamoyl group or a chalconyl group.

In this way, a confetti-like structure in which a plurality of second fine particles 22 formed with a second film compound film are bonded and fixed to the surface of the first fine particles 21 formed with a film of the first film compound. Composite fine particles 11 are obtained (see FIG. 2). In the figure, the thicknesses of the coatings of the first and second film compounds are exaggerated. Actually, the thicknesses of these coatings are negligible with respect to the size of the composite fine particles 11. The composite fine particles 11 may be used as they are in the production of the super water / oil repellent antifouling translucent film 10, but further heated to fuse the first fine particles 21 and the second fine particles 22 into the composite fine particles 11 a. It may be prepared and used for the production of the super water / oil repellent antifouling translucent film 10. The fusion can be performed by heating for a predetermined time at a temperature not lower than the softening temperature and not higher than the melting point of the first fine particles 21 and the second fine particles 22. At that time, the coatings of the first and second film compounds disappear due to thermal decomposition and / or oxidative decomposition.
When the composite fine particles 11 are used as they are for the production of the super water / oil repellent antifouling translucent film 10, the first or second reactive group becomes a surface functional group, so that the surface reaction reacting therewith. It is necessary to select a membrane compound having a group. In the case where the first or second reactive group is an amino group, an alkoxysilyl group can be used as the surface reactive group. In the case of an epoxy group, a chlorosilyl group may be used as the surface reactive group.

The abrasion-resistant super water- and oil-repellent translucent film 100 according to the second embodiment of the present invention generates a binder that can be bonded to the surface of the film substrate 101 by evaporation of the solvent and subsequent heating. A dispersion in which spherical or substantially spherical fine particles 102 are dispersed in a solvent containing a precursor is applied to the surface of the film substrate 101, the solvent is evaporated, and a binder precursor is formed on the surfaces of the film substrate 101 and the fine particles 102. 103a is generated, and a part of the surface of the binder precursor 103a generated on the surface of the fine particles 102 is etched, and the surface of the fine particles 102 attached or bonded to the surface of the film substrate 101 through the binder The step b of forming a plurality of spherical or substantially spherical protrusions 104 smaller than the fine particles 102 and the fine particles 102 on the surface via the binder precursor 103a A process c for heating and adhering or bonding the film substrate 101 to bond and fix the fine particles 102 with the protrusions 104 formed on the surface of the film substrate 101 through the generated binder 103, and fine particles with the protrusions 104 formed A step d of forming a water / oil repellent / antifouling thin film (not shown) on the surface of the resin film substrate 101 to which 102 is bonded and fixed (see FIG. 3).
Hereinafter, each process will be described in more detail.

Step a
Except for using the spherical or substantially spherical fine particles 102 instead of the composite fine particles, the binder precursor is used in step D of the method for manufacturing the wear-resistant super water / oil repellent translucent film 10 according to the first embodiment of the present invention. This is the same as the case of using the dispersion liquid containing the body.

As for the resin film substrate 101 and the fine particles 102, the film surface layer 14 and the first fine particles 21 used for the production of the abrasion-resistant super water- and oil-repellent translucent film 10 according to the first embodiment of the present invention. And the same for each. The solvent and binder precursor used for the production of the dispersion and the coating conditions are the same as those in step D of the method for producing the wear-resistant super water- and oil-repellent translucent film 10 according to the first embodiment of the present invention. It is.
In place of the spherical or substantially spherical fine particles 102, the composite fine particles 11 or the fused composite fine particles used in the production of the abrasion-resistant super water- and oil-repellent translucent film 10 according to the first embodiment of the present invention. 11a (see FIG. 2) may be used.

Step b
Next, a part of the surface of the binder precursor 103a generated on the surface of the fine particles 102 is etched, and a plurality of particles smaller than the fine particles 102 are attached to the surface of the fine particles 102 attached or bonded to the surface of the film substrate 101 through the binder. A spherical or substantially spherical protrusion 104 is formed. The size of the protrusion 104 to be formed is 1/100 or more and 1/5 or less of the diameter of the fine particles, and is 1 nm to 50 μm, preferably 5 nm to 80 nm, more preferably 5 to 50 nm. In particular, for the production of a wear-resistant super water- and oil-repellent translucent film 100 that requires transparency for use in glass windows, solar energy utilization devices, optical devices, display devices, etc., scattering of incident light In order to suppress a decrease in transparency due to or irregular reflection, the size of the protrusions needs to be 400 nm or less shorter than the wavelength of visible light and 1/100 or more and 1/5 or less of the diameter of the fine particles.
Examples of the etching method that can form fine protrusions with the above-described size include a dry etching method using high-density plasma generated from a reactive gas.
As shown in FIG. 3, the surface of the binder 103 formed on the surface of the film substrate 101 may also be etched.

Process c
The film substrate 101 having the fine particles 102 (or the composite fine particles 11 or the fused composite fine particles 11a) attached or bonded to the surface via the binder precursor 103a was heated to form the projections 104 via the generated binder 103. The fine particles 102 may be bonded and fixed to the surface of the film substrate 101. Here, even if the step c was performed before the step b, a similar surface shape could be formed.

Step d
Finally, a water- and oil-repellent and antifouling thin film having a nano-level film thickness is formed on the surface of the film substrate 101 to which the fine particles 102 having the protrusions 104 are bonded and fixed. About this process, it is the same as that of the process E of the manufacturing method of the abrasion-resistant super water- and oil-repellent translucent film 100 which concerns on the 1st Embodiment of this invention.

The super water / oil repellent antifouling translucent film 10 has a water droplet contact angle of about 150 degrees. From the study results using various volumes of water droplets (0.02 to 0.08 mL), it was confirmed that when the water droplet contact angle is 150 degrees or more, the falling angle is 15 degrees or less regardless of the volume of the water droplet. Yes. Therefore, when the super water / oil repellent antifouling and translucent films 10 and 100 are attached to the surface of a window glass plate of a vehicle or a building, most of the water droplets cannot fall on the surface and fall down.

The super water / oil repellent / antifouling translucent films 10 and 100 are excellent in durability such as abrasion resistance and weather resistance, water-dropping property (sliding property), and antifouling property. It can be attached to the surface of glass windows of vehicles and buildings that require a dirty function. Vehicles that can use glass windows with super water and oil repellent antifouling and translucent films 10 and 100 used include automobiles, railway vehicles, ships, etc. It can be used as a glass plate for any window. In particular, when used for a glass window for a driver's seat, it also has an effect of improving visibility from the driver's seat. Moreover, as a building which can use the glass window which stuck super water and oil repellent antifouling translucent films 10 and 100, arbitrary buildings, such as a detached house, an apartment house, an office building, are mentioned. .

Further, when a glass plate with a super water / oil repellent antifouling translucent film 10 or 100 attached thereto is used as a face plate of a solar energy utilization device, solar energy due to adhesion of dirt, scattering of incident light, irregular reflection, etc. The solar energy utilization apparatus which can suppress the fall of the utilization efficiency of this, is excellent in durability and a weather resistance, and can be used over a long period of time also in the severe outdoors environment is provided. Specific examples of the solar energy utilization device include a solar water heater, a solar battery, and a greenhouse.

Further, the super water / oil / oil repellent and light-transmitting translucent films 10 and 100 can also be applied to members for optical devices that require a water / oil / oil repellent and antifouling function. As a member for optical equipment, a lens such as a camera and a spectrometer, a prism, and a mirror can be used. Examples of the display device include a face plate of a display device such as a PDP, and the like. Water and oil repellent excellent in durability such as abrasion resistance and weather resistance, water droplet water separation (also referred to as water slidability), and antifouling properties. An antifouling antireflection film can be formed, and an optical device excellent in optical performance, a face plate of a display device such as a PDP display with less surface reflection, and the like can be provided.

Next, examples carried out for confirming the effects of the present invention will be described. These examples are illustrative only and are not intended to limit the scope of the invention.
Example 1: Production of super water / oil repellent antifouling translucent film (1)
(1) Preparation of fused composite fine particles [1] Production of epoxidized silica fine particles 3-Glycidyloxypropyltrimethoxysilane (Chemical Formula 6) 0.99 parts by weight and dibutyltin bisacetylacetonate (condensation catalyst) 0.01 weight A part was weighed and dissolved in 100 parts by weight of a hexamethyldisiloxane solvent to prepare a reaction solution.

The first silica fine particles having an average diameter of about 130 nm were dispersed in the reaction solution thus obtained, and reacted for about 2 hours in the air (relative humidity 45%) while stirring.
Thereafter, it was washed with ethanol to remove excess alkoxysilane compound and dibutyltin bisacetylacetonate.

[2] Preparation of Aminated Silica Fine Particles Weigh 0.99 parts by weight of 3-aminopropyltrimethoxysilane (Chemical Formula 7, manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.01 parts by weight of acetic acid (condensation catalyst). A reaction solution was prepared by dissolving in 100 parts by weight of hexamethyldisiloxane solvent.

The second silica fine particles having an average diameter of about 15 nm were dispersed in the reaction solution thus obtained, and reacted in the air (relative humidity 45%) for about 2 hours while stirring.
Thereafter, it was washed with ethanol to remove excess alkoxysilane compound and dibutyltin bisacetylacetonate.

[3] Preparation of fused composite fine particles Epoxidized silica fine particles and aminated silica fine particles are uniformly mixed, heated at 100 ° C. for 30 minutes, reacted with epoxy groups and amino groups, and a plurality of epoxidized silica fine particles are formed on the surface of the epoxidized silica fine particles. Composite fine particles to which aminated silica fine particles were bound and fixed were prepared. Next, the aminated silica fine particles were fused to the surface of the epoxidized silica fine particles by heating at 630 ° C. for 25 minutes to prepare fused composite fine particles.

(2) Embedding of fused composite fine particles into the film surface layer After uniformly spreading the fused composite fine particles prepared as described above onto the surface of the PET film, the PET film is heat-softened and fused using a roll. Fine particles were injected.

After weighing 99 parts by weight of heptadecafluorodecyltrimethoxysilane CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , 1 part by weight of dibutyltin diacetylacetonate (condensation catalyst), A reaction solution having a concentration of about 1% by weight was dissolved in siloxane. The reaction solution was applied to the surface of the film surface layer in which the fused composite fine particles were embedded, and reacted at room temperature. At this time, since the surface of the fused composite fine particles and the silica coating contains a large number of hydroxyl groups, the heptadecafluorodecyltrimethoxysilane-Si (OCH ₃ ) group and the hydroxyl group are removed in the presence of the condensation catalyst. Alcohol (in this case, de-CH ₃ OH) was reacted to form a bond as shown in the following chemical formula (Chemical Formula 8), and the water- and oil-repellent and antifouling thin film containing a fluorocarbon group was chemically bonded to the surface. The film was formed in a thickness of about 1 nanometer.

Then, the excess reaction solution was washed and removed with dichloromethane, and it was covered with a water / oil repellent / antifouling thin film (monomolecular film) containing a fluorocarbon group chemically bonded to the surface of the fused composite fine particles exposed on the surface. In addition, a super water and oil repellent and antifouling translucent film for a solar water heater having water and oil repellent and antifouling properties and an antireflection function could be produced. FIG. 4 shows a scanning electron microscope (SEM) photograph of the surface of the abrasion-resistant super water / oil repellent / antifouling translucent film thus obtained. As the composite fine particles of the fusion are embedded in the film surface layer, complex irregularities are formed on the surface. As will be described later, a water- and oil-repellent and antifouling thin film is formed on the surface of the flat film surface layer. It was confirmed that a water droplet contact angle of 155 ± 8 degrees, which is superior in water repellency, oil repellency and antifouling property, can be realized as compared with a water droplet contact angle of about 110 degrees. Moreover, since the size of the fused composite fine particles used for the production was all shorter than the wavelength of visible light, the transparency was hardly deteriorated.

On the other hand, at this time, the formed water- and oil-repellent and antifouling thin film on the surface of the fine particles has the effect of reducing the surface energy of the silica fine particles, and the apparent surface of the substrate surface along with the unevenness having a fractal structure. It has the effect of greatly reducing energy. When the water droplet contact angle was actually measured, although some variation was observed, the contact angle was about 150 to 160 ° and the critical surface energy was about 1 to 3 mN / m.

When the super water / oil / oil repellent translucent film obtained in this way was installed in a solar water heater and tested for practical use, it was almost free from dirt and dust from the air, and it rained. If it is self-cleaning, the surface reflection of the film can be reduced by fine surface irregularities, and the average value of the heat collection efficiency is about 3% or more on average compared to the case where ordinary glass (transmittance of about 92%) is attached. I was able to improve. In the case of ordinary glass, the surface becomes dirty after 1 year of use, and the light utilization efficiency is reduced by about 30%. However, the solar water heater using the face plate glass with this film installed becomes dirty even after 1 year. The efficiency reduction due to was less than 5%.

Example 2: Production of super water / oil repellent antifouling translucent film (2)
Except for using epoxidized silica fine particles having different diameters (mixing silica fine particles having an average diameter of 100 nm and silica fine particles having an average diameter of 50 nm in a weight ratio of about 1:10). Using the same method as in Example 1, a super water / oil / oil repellent and light transmissive film was prepared. When this is attached to the surface of the solar cell panel, the cross section near the surface of the solar cell has a fractal structure, a high water / oil repellency effect (158 ° in water droplet contact angle), and high light transmittance (light of around 500 nm). A solar cell covered with a super water / oil / oil repellent and light-transmitting film having an antireflection function having a transmittance of about 99%) could be produced. Furthermore, as a result of the practical application test in this cell, even after half a year, dirt in the air and dirt due to yellow sand hardly adhere, and if it rains, it is self-cleaned, and further, the film is formed by fine surface unevenness As a result, the light utilization efficiency can be improved by about 6% on average as compared with the case where an ordinary glass plate is attached. In the case of ordinary glass, the surface becomes dirty after one year of use, and the light utilization efficiency is reduced by about 30%. However, in the solar cell using the face plate glass on which this film is installed, the surface is stained even after one year. There was almost no decrease in efficiency. Although the water droplet contact angle at this time was about 158 °, practically similar effects were obtained when the water droplet contact angle was 140 ° or more.

Example 3: Production of super water and oil repellent antifouling translucent film (3)
Using the same method as in Example 1, a lens having a water / oil repellent antifouling antireflective coating was fabricated and mounted on an optical device for testing purposes. There was almost no adhesion, and the light transmittance was the same as that of the anti-reflection multi-coated film, and the lens was excellent in antifouling property without being inferior in optical characteristics.

Example 4: Production of super water / oil repellent antifouling translucent film (4)
A PDP (Plasma Display Panel) face plate with a water / oil / oil repellent / anti-fouling anti-reflective coating formed on the surface using the same method as in Example 1 was tested and used. In addition, it was possible to efficiently reduce the reflection of indoor fluorescent lamps and the like onto the face plate surface, and the visibility was greatly improved. The transmittance was 92% or more over the entire wavelength region of visible light.

Example 5: Production of super water- and oil-repellent antifouling light-transmitting film (5)
Silica fine particles having an average diameter of about 130 nm were dispersed in a methanol solution of methyltrimethoxysilane and applied to the surface of the PET film. By heating at a temperature not lower than 70 ° C. and not higher than the softening temperature of the PET film, methyltrimethoxysilane was polycondensed, and silica fine particles could be fixed on the surface of the PET film through the formed transparent polysiloxane film. . Next, the polysiloxane film is dry-etched using a plasma method (plasma gas: CF ₄ —CF ₂ F ₂ —O ₂ : pressure 0.4 Pa), whereby the diameter of the bottom surface on the surface of the silica fine particles is about several tens of nm. A substantially hemispherical unevenness was formed. The surface of the PET film having the polysiloxane-based clear coat layer on which the confetti-like irregularities are obtained in this way is subjected to the same operation as in Example 1, and is about 1 nm thick that is chemically bonded to the surface. A water and oil repellent antifouling thin film containing a fluorocarbon group was formed. In this way, as in Example 1 and the like, a super water- and oil-repellent and antifouling translucent film having high water repellency with a water droplet contact angle of about 160 ° and excellent in oil repellency and antifouling properties. Could be manufactured. The obtained super water / oil repellent antifouling and translucent film had a high transmittance of 92% or more in the entire wavelength range of visible light.

The super water- and oil-repellent and antifouling light-transmitting film of the present invention has glass and windows for buildings and vehicles, solar water heaters, solar water-repellent films that require durability and weather resistance in addition to water repellency, oil repellency and antifouling properties. It can be favorably applied to a condensing member of a solar energy utilization device such as a battery and a greenhouse, an optical device and a display device, particularly a face plate of a touch panel display having excellent fingerprint resistance.

DESCRIPTION OF SYMBOLS 10,100 Super water-repellent oil-repellent antifouling light-transmitting film 11 Composite fine particle 11a Fusion composite fine particle 13 Protrusion 14 Film surface layer 14a Film surface layer 15 with confetti-like protrusion formed Surface reactive group and fluorocarbon group Water-repellent / oil-repellent antifouling thin film 21 First fine particles 22 with a film of a first film compound 22 Second fine particles 101 with a film of a second film compound 102 Fine particles 103 Binder 103a Binder precursor 104 Protrusion

Claims (24)

A film surface layer made of a translucent material;
It is embedded in the film surface layer so that at least a part of the surface is exposed, and the surface of a spherical or substantially spherical fine particle is formed with a plurality of spherical or substantially hemispherical protrusions having a diameter smaller than that of the fine particle. Transparent composite fine particles having a structure; and
Have a water-repellent oil-repellent antifouling film coupled formed so as to cover at least a part of the surface of the composite fine particles exposed from the film surface layer,
The film surface layer has a first reactive functional group;
The composite fine particles have a second reactive functional group that reacts with the first reactive functional group to form a bond;
The composite fine particles are bonded and fixed to the film surface layer through bonds formed by the reaction of the first and second reactive functional groups, and are characterized by super water and oil repellency and antifouling properties Translucent film. The fine particles have a diameter of 50 to 100 nm,
2. The transparent super water / oil repellent antifouling translucent film according to claim 1, wherein the protrusion has a diameter of 10 to 20 nm. 3. The super water- and oil-repellent and antifouling light-transmitting property according to claim 1, wherein the fine particles and the protrusions are made of a material selected from the group consisting of glass, silica, alumina and zirconia. the film. Said first and second reactive functional group, claim 1, characterized in that both a functional group which does not react dimerization under production conditions of the super water-repellent, oil-repellent antifouling translucent film 4. The super water / oil repellent antifouling translucent film according to any one of 3 above. Super water-repellent, oil-repellent antifouling translucent film according to any one of claims 1 to 3, characterized in that the critical surface energy of the surface is less than 1 mN / m or more 3 mN / m. At least a part of the transparent composite fine particles having a confetti-like structure in which a plurality of spherical or hemispherical protrusions having a smaller diameter than the fine particles are formed on the surface of the spherical or substantially spherical fine particles are exposed on the surface. And step D of embedding in the film surface layer having translucency,
It possesses a step E of forming the water repellent oil repellent antifouling thin film on the surface of the composite fine particles exposed from the film surface layer,
The composite fine particles,
A first film compound having a first surface reactive group that reacts with a surface functional group of a spherical or substantially spherical first fine particle to form a bond, and a first film compound having a first reactive group at both ends, respectively. The reaction liquid is brought into contact with the surface of the first fine particle, and the first liquid is bonded and fixed to the surface of the first fine particle through a bond formed by a reaction between the surface functional group and the surface reactive group. Forming a film of the film compound;
A second surface reactive group that reacts with a surface functional group of a second fine particle that is spherical or substantially spherical and has a smaller diameter than the first fine particle, and reacts with the first reactive group. A second reaction liquid containing a second film compound having a second reactive group that forms a bond at both ends is brought into contact with the surface of the second fine particle, and the surface functional group, the surface reactive group, Forming a film of the second film compound that is bonded and fixed to the surface of the second fine particle through the bond formed by the reaction of
The first fine particles on which the first film compound film is formed and the second fine particles on which the second film compound film is formed are brought into contact with each other, and the first reactive group and the first fine particles are brought into contact with each other. A plurality of coatings of the second film compound formed on the surface of the first fine particles on which the coating of the first film compound has been formed through a bond formed by reacting with two reactive groups. A method for producing a super water- and oil-repellent and antifouling light-transmitting film, comprising the step C of preparing a confetti-like composite fine particle to which the second fine particles are bonded and fixed . The diameter of the first fine particle is 50 to 100 nm, the diameter of the second fine particles of ultra-water-repellent, oil-repellent antifouling translucent film according to claim 6, wherein it is 10~20nm Production method. 8. The super-water-repellent / repellent repellent according to claim 6 or 7 , wherein in the step C, the prepared composite fine particles are further heat-treated to fuse the second fine particles to the surface of the first fine particles. Manufacturing method of oil-proof antifouling translucent film. After the step C, the second fine particles formed with the second film compound coating not fixed to the surface of the first fine particles formed with the first film compound coating are washed. method for manufacturing ultra-water-repellent, oil-repellent antifouling translucent film of any one of claims 6 8, characterized in that removal. In the step E, a third surface-reactive group that reacts with any one or more of the functional groups present on the film surface layer and the surface of the composite fine particle to form a bond and a fluorocarbon group. Any of functional groups present on the surface of the film surface layer and the composite microparticles are brought into contact with the surface of the film surface layer to which the composite microparticles are bonded and fixed. from claim 6, characterized by forming a film of said third film compound bound secured to the surface via a bond formed by the reaction of one or more and said third surface reactive groups 9 The method for producing a super water / oil repellent antifouling translucent film according to any one of the above. The first to third surface reactive groups are alkoxysilyl groups, the first and second reaction liquids, and the water / oil repellent / antifouling treatment liquid,
(1) one or more compounds selected from the group consisting of carboxylic acid metal salts, carboxylic acid ester metal salts, carboxylic acid metal salt polymers, carboxylic acid metal salt chelates, titanate esters and titanate ester chelates, and / or Or (2) one or more compounds selected from the group consisting of ketimine compounds, organic acids, aldimine compounds, enamine compounds, oxazolidine compounds, and aminoalkylalkoxysilane compounds as a condensation catalyst. 1 0 manufacturing method of super-water-repellent, oil-repellent antifouling translucent film according. Preparation of the after step E, ultra water-repellent, oil-repellent antifouling translucent film according to claim 1 0 or 1 1, wherein the washing removes the excess water-repellent oil-repellent antifouling treatment solution Method. Spherical or substantially spherical fine particles in a solvent containing a binder precursor that generates a binder that can be bonded to the surface of the film substrate by evaporation of the solvent and subsequent heating, or the fine particles on the surface of the spherical or substantially spherical fine particles After applying a dispersion liquid in which a slab-like composite fine particle in which a plurality of spherical or hemispherical projections having a smaller diameter are bonded and fixed is applied to the surface of the film substrate, the solvent is evaporated and the binder precursor is passed through the binder precursor. A step of binding and fixing the fine particles or the composite fine particles to the surface of the film surface layer;
The fine particles or the composite fine particles and / or the fine particles adhered to or bonded to the surface of the film substrate through the binder precursor by etching a part of the surface of the binder generated on the surface of the film substrate. Or a step b of forming a plurality of spherical or substantially spherical protrusions smaller than the fine particles on the surface of the composite fine particles and / or the film substrate;
The film base material having the fine particles or the composite fine particles attached or bonded to the surface via the binder precursor is heated, and the fine particles on which the protrusions are formed via the generated binder are formed on the film base material. A step c for bonding and fixing to the surface;
Possess a step d to form a water-repellent oil-repellent antifouling thin film on the surface of the film substrate, wherein the fine particles are connected and fixed,
The film substrate, the fine particles, and the binder are all transparent, and the height of the confetti formed on the surface of the film substrate in the step c is 30 to 300 nm. A method for producing a water- and oil-repellent antifouling light-transmitting film. Claim 1 3 manufacturing method of super-water-repellent, oil-repellent antifouling translucent film, wherein a diameter of said fine particles is 50 to 100 nm. As a method of etching a part of the surface of the binder, the production method according to claim 1 3 or 1 4 SL placing super water-repellent, oil-repellent antifouling translucent film, which comprises using a chemical etching or physical etching. The heating temperature in the step c is the film that substrate is less than the softening point claims 1 to 3, characterized in 1 5 according to any one of the super-water-repellent, oil-repellent antifouling translucent film Production method. In the step d, a film repelling comprising a film compound having a surface reactive group and a fluorocarbon group that reacts with any one or more of the functional groups present on the surface of the film substrate and the composite fine particles to form a bond. A water / oil repellent antifouling treatment solution is brought into contact with the surface of the film base material on which the composite fine particles are bonded and fixed, and one or more of functional groups present on the surface of the film base material and the composite fine particles and the surface super repellent of any one of claims 1 3 to 16, characterized by forming a film of the film compound bound fixed to the surface through the formed bonds by reaction with the reactive group Manufacturing method of oil-proof antifouling translucent film. The surface reactive group is an alkoxysilyl group, and the water / oil repellent / antifouling treatment liquid is:
(1) one or more compounds selected from the group consisting of carboxylic acid metal salts, carboxylic acid ester metal salts, carboxylic acid metal salt polymers, carboxylic acid metal salt chelates, titanate esters and titanate ester chelates, and / or Or (2) one or more compounds selected from the group consisting of ketimine compounds, organic acids, aldimine compounds, enamine compounds, oxazolidine compounds, and aminoalkylalkoxysilane compounds as a condensation catalyst. 18. A process for producing a super water / oil repellent antifouling light transmissive film according to 17 . 19. The method for producing a super water / oil / oil repellent / fouling and translucent film according to claim 17 or 18, wherein the excess water / oil / oil / repellency / antifouling treatment liquid is washed away after the step d. Manufacturing method of the step super water-repellent, oil-repellent antifouling translucent film of any one of claims 1 3 to 19, characterized in that performing the c before the step b. Any one super water-repellent, oil-repellent antifouling translucent film glass window with as claimed in claim 1 5. The solar energy utilization apparatus which has a super water-repellent oil-repellent antifouling light-transmitting film of any one of Claim 1 to 5 . Optical apparatus having a super water-repellent, oil-repellent antifouling translucent film of any one of claims 1 5. A display device having a super water-repellent, oil-repellent antifouling translucent film of any one of claims 1 5.