Patent Grant
9321044
The present invention relates to a catalyst-supporting porous film, a catalyst member, an air cleaning device, and a catalyst-supporting porous film manufacturing method.
Photocatalysts are capable of decomposition of organic substances and hydrophilization of a film surface and have been employed for uses including surface cleaning, deodorization, antimicrobial treatments, etc. Usually, catalyst particles, such as titanium oxide particles, are dispersed in a dispersion, and this dispersion is applied over a base and dried, whereby a film which has catalyst particles supported thereon is formed. In general, the catalytic effect increases according to the surface area of this film. Therefore, forming a catalyst-supporting film such that the surface of the film has an uneven structure has been considered (see Patent Documents 1 to 4).
Patent Document 1 discloses that a coating agent, which is a mixture of photocatalyst particles and a binder resin, is applied over a base which has a surface with minute unevenness so as to form a coating layer over the surface of the base. However, applying the coating agent over the uneven surface of the base in such a way leads to that the catalyst particles are caught in recessed portions so that the catalytic effects would not efficiently increase in some cases.
On the other hand, Patent Documents 2 to 4 disclose that a mixture (dispersion) is applied over a surface of a base, and thereafter, a surface of the mixture is deformed so as to have an uneven structure. Specifically, Patent Document 2 discloses forming an uneven structure which has a cleaning function and an antireflection function over a lens. Patent Document 3 discloses using a porous alumina layer formed by anodization as a mold so as to form a minute uneven pattern in an inorganic material which has a photocatalytic property. Patent Document 4 discloses a photocatalytic layer which has a moth-eye structure in order to realize a low reflection property. In this way, a surface of a film which has catalyst particles supported thereon is deformed into a porous shape, whereby the catalytic action can be increased.
The catalyst-supporting films of Patent Documents 1 to 4 have relatively large surface areas and exhibit relatively high catalytic effects. However, in order to further increase the catalytic effect, it is necessary to increase the number of catalyst particles which are present in the vicinity of the surface of the catalyst-supporting film rather than increasing the surface area of the catalyst-supporting film. However, simply increasing the number of catalyst particles dispersed in the dispersion for the purpose of increasing the number of catalyst particles leads to reduction in adhesion between the catalyst particles, so that the catalyst-supporting film can be fragile.
The present invention was conceived in view of the above problems. One of the objects of the present invention is to provide a catalyst-supporting porous film which has a high catalytic effect, a catalyst member, an air cleaning device, and a catalyst-supporting porous film manufacturing method.
A catalyst-supporting porous film of the present invention includes: a resin layer; and catalyst particles dispersed in the resin layer, wherein the catalyst particles are unevenly distributed so as to be present at a surface of the resin layer.
In one embodiment, the catalyst-supporting porous film includes a porous section and a supporting section for supporting the porous section, and the number of catalyst particles per unit volume in the porous section is greater than the number of catalyst particles per unit volume in the supporting section.
In one embodiment, the catalyst-supporting porous film has a surface of a moth-eye structure or inverted moth-eye structure.
In one embodiment, the surface has a plurality of minute raised portions and a saddle portion extending between vertexes of adjacent two of the plurality of minute raised portions.
In one embodiment, the resin layer contains a photocurable resin.
In one embodiment, the resin layer contains a plurality of thermoplastic resins which are phase-separated from one another.
In one embodiment, the catalyst particles include titanium oxide particles.
In one embodiment, the catalyst particles include zinc-supporting titanium oxide particles.
In one embodiment, a through hole is provided.
A catalyst member of the present invention includes: a base which has a principal surface; and a catalyst-supporting porous film provided on the principal surface of the base.
A catalyst member of the present invention includes: a base which has two principal surfaces; and a catalyst-supporting porous film provided on each of the two principal surfaces of the base.
An air cleaning device of the present invention includes: the above-described catalyst-supporting porous film; and an ion generating device for generating a positive ion and a negative ion.
A catalyst-supporting porous film manufacturing method of the present invention includes the steps of: providing a mixture which contains catalyst particles, a resin, and a solvent; applying the mixture on a base and drying the mixture; and deforming a surface of the dried mixture into a porous shape, wherein the step of drying includes forming a resin layer from the mixture, in which the catalyst particles being dispersed, and the catalyst particles are unevenly distributed so as to be present at a surface of the resin layer.
In one embodiment, in the step of providing, the resin contains a photocurable resin, and the step of deforming into the porous shape further includes curing the photocurable resin with a mold being pressed against the mixture.
In one embodiment, in the step of curing, the mold has a surface of a moth-eye structure or inverted moth-eye structure.
According to the present invention, a catalyst-supporting porous film which has a high catalytic effect, a catalyst member, an air cleaning device, and a catalyst-supporting porous film manufacturing method can be provided.
Hereinafter, embodiments of a catalyst-supporting porous film, a catalyst member, an air cleaning device, and a catalyst-supporting porous film manufacturing method of the present invention are described with reference to the drawings. Note that, however, the present invention is not limited to the embodiments which will be described below.
An embodiment of a catalyst-supporting porous film of the present invention is described with reference to
In the catalyst-supporting porous film 10 of the present embodiment, the catalyst particles 14 are unevenly distributed so as to be present at the surface of the resin layer 12. For example, almost all of the surface of the resin layer 12 is covered with the catalyst particles 14. Since the catalyst-supporting porous film 10 including the catalyst particles 14 is a porous film which has a relatively large surface area and the catalyst particles 14 are unevenly distributed so as to be present at the surface of the resin layer 12, the catalytic effect can be efficiently increased. Note that, in this specification, the catalyst-supporting porous film 10 is sometimes simply referred to as “catalyst-supporting film 10” or “film 10”.
The catalyst-supporting film 10 includes a porous section 22 which has a porous shape and a supporting section 24 for supporting the porous section 22. Here, a plurality of raised portions are defined by the porous shape of the porous section 22. The raised portions have a conical shape or a bell-like shape. Such a structure is also referred to as “moth-eye structure”.
Although its size is not precisely shown in
For example, when the catalyst particles 14 are titanium oxide particles, the catalyst-supporting film 10 exhibits relatively strong oxidizing effect and hydrophilic effect. On the other hand, when the catalyst particles 14 are zinc-supporting titanium oxide particles, the catalyst-supporting film 10 exhibits slightly low oxidizing effect and hydrophilic effect as compared with the case where the catalyst particles 14 are titanium oxide particles. Note that, however, slightly reducing the oxidizing effect of the catalyst particles 14 enables to prevent deterioration and discoloration of the resin layer 12 in which the catalyst particles 14 are dispersed. When the catalyst particles 14 are zinc-supporting titanium oxide particles, the catalyst-supporting film 10 exhibits an oxidizing effect to some extent even if the catalyst-supporting film 10 is not irradiated with light. Therefore, decomposition and deodorization of organic substances can be achieved.
The resin layer 12 may be made of an inorganic resin or may be made of an organic resin. When the catalyst particles 14 are photocatalyst particles (for example, titanium oxide particles), from the viewpoint of preventing decomposition of the resin layer 12 by the catalyst particles 14, the resin layer 12 is preferably made of an inorganic resin. From the viewpoint of retention of the catalyst particles 14 and durability of the catalyst-supporting film 10, the resin layer 12 is preferably made of an organic resin. Alternatively, for example, the resin layer 12 may be made of a fluoric resin. When the catalyst particles 14 are zinc-supporting titanium oxide particles, decomposition of the resin layer 12 by the catalyst particles 14 is relatively unlikely to occur. Therefore, the resin layer 12 is preferably made of an organic resin.
Hereinafter, a method for manufacturing the catalyst-supporting film 10 of the present embodiment is described with reference to
First, as shown in
For example, the catalyst particles 14 are titanium oxide particles. Alternatively, the catalyst particles 14 used may be zinc-supporting titanium oxide particles. For example, the zinc-supporting titanium oxide particles used may be Atomy Ball TZ-R available from JGC Catalysts and Chemicals Ltd. Atomy Ball TZ-R contains zinc and titanium oxide and has average particle diameter of about 10 nm. The catalyst particles 14 may be provided with a surface treatment. For example, the surface treatment may be carried out using a coupling agent, such as a silane coupling agent.
In general, the surface of inorganic oxide microparticles or metal catalyst-supporting inorganic oxide microparticles that constitute the catalyst particles 14 is hydrophilic. The degree of the hydrophilicity of the catalyst particles 14 can be modified by a surface treatment. The resin preferably contains a resin whose hydrophilicity is higher than that of the catalyst particles 14.
The resin may contain a curable resin or may contain a thermoplastic resin. The curable resin may be a thermosetting resin or may be a photocurable resin. The curable resin advantageously has high hardness and high mechanical strength. The photocurable resin (including UV-curable resins and electron beam curable resins) advantageously has a fast curing speed. The resins which may be used in the embodiments of the present invention are disclosed in Japanese Laid-Open Patent Publication No. 2009-128488, for example. The entire disclosures of Japanese Laid-Open Patent Publication No. 2009-128488 are incorporated by reference in this specification.
Examples of the thermoplastic resin include styrene resins, (meth)acrylic resins, organic acid vinyl ester resins, vinyl ether resins, halogen-containing resins, olefin resins (including alicyclic olefin resins), polycarbonate resins, polyester resins, polyamide resins, thermoplastic polyurethane resins, polysulfone resins (polyethersulfones, polysulfones, and the like), polyphenylene ether resins (2,6-xylenol polymers, and the like), cellulose derivatives (cellulose esters, cellulose carbamates, cellulose ethers, and the like), silicone resins (polydimethyl siloxanes, polymethyl phenyl siloxanes, and the like), and rubbers or elastomers (diene rubbers such as polybutadienes, polyisoprenes, and the like, styrene-butadiene copolymers, acrylonitrile-butadiene copolymers, acrylic rubbers, urethane rubbers, silicone rubbers, etc.). These thermoplastic resins may be used solely, or two or more of them may be used in combination.
Examples of the thermosetting resin include epoxy resins, unsaturated polyester resins, urethane resins and silicone resins which have an epoxy group, an isocyanate group, an alkoxysilyl group, a silanol group, a polymeric group (such as a vinyl group, an allyl group, a (meth)acryloyl group), or the like.
The photocurable resin used may be selected from a wide variety of monomers and oligomers which are curable by an active light ray (ultraviolet ray, visible ray, electron beam, etc.). The photocurable resin may be, for example, a monomer and/or oligomer which has a vinyl group, an allyl group, a (meth)acryloyl group), or a photosensitive group (such as a cinnamoyl group). For example, an acrylic or methacrylic monomer and/or oligomer may be suitably used. The monomer or oligomer may be monofunctional or may be polyfunctional (i.e., may have 2 to 6 polymeric groups). A monomer and an oligomer may be appropriately mixed. Alternatively, a monofunctional monomer or oligomer and a polyfunctional monomer or oligomer may be mixed. Further, when necessary, an initiator, a polymerization promoter, and/or a polymerization inhibitor may be mixed.
The base 30 may be a glass substrate. Alternatively, the base 30 may be a film which is made of triacetyl cellulose (TAC), acryl or polyethylene terephthalate (PET).
Then, as shown in
During the drying, the solvent contained in the mixture is vaporized, whereby the resin layer 12 is formed in which the catalyst particles 14 are dispersed. Although details will be described later, the catalyst particles 14 inside the mixture A move to the surface of the mixture A with the progress of the drying, so that the catalyst particles 14 are unevenly distributed so as to be present at the surface of the resin layer 12. Note that, as a result of the drying, an uneven structure may be formed in the surface of the resin layer 12.
Then, as shown in
Thereafter, as shown in
When the catalyst-supporting film 10 has a surface of a moth-eye structure, the surface area S of the catalyst-supporting film 10 is expressed as shown below. Here, a moth-eye structure is assumed in which circular cones with radius r and height h are arranged in a close-packed arrangement on a square supporting section with length x on each side.
S=x2+(int(x/(2r)))2×(πr(r2+h2)1/2−πr2)
where int( ) represents the integer part of the number in the parentheses.
The mold 80 is suitably manufactured using a porous alumina layer. Hereinafter, an example of the method for manufacturing the mold 80 is described with reference to
First, as shown in
Then, the aluminum film 80a is anodized so as to form a porous alumina layer 80b which has micropores 80p extending perpendicular to the surface of the aluminum film 80a as shown in
For example, the anodization may be realized by immersing a base in an acidic electrolytic solution of sulfuric acid, oxalic acid, phosphoric acid, or the like, or an alkaline electrolytic solution, and applying a voltage with the base being used as an anode. In this process, the average distance between the centers of adjacent micropores and the depth of the micropores vary depending on the conditions of the anodization. Note that the average distance between the centers of adjacent micropores is approximately twice the thickness of a barrier layer, and is approximately proportional to the voltage that is applied during the anodization. The pore diameter of the micropores depends on the type, concentration, temperature, etc., of the electrolytic solution. The micropores are preferably arranged with a regularity degraded to some extent. Note that, however, the micropores may be in an irregular (i.e., non-periodic) arrangement or may be in a regular arrangement.
For example, in the case where the average distance between the centers of adjacent micropores 80p is about 180 nm, the anodization is performed for 25 seconds with the forming voltage of 80 V using an electrolytic solution of 0.6 wt % oxalic acid at the solution temperature of 5° C. In the case where this average distance is 400 nm, the anodization is performed for 30 to 45 seconds with the forming voltage of 200 V using an electrolytic solution of 2 wt % tartaric acid at the solution temperature of 5° C.
Then, the etching is performed, whereby the pore diameter of the micropores 80p is increased as shown in
Then, the aluminum film 80a is again partially anodized such that the micropores 80p are grown in the depth direction and the thickness of the porous alumina layer 80b is increased as shown in
Thereafter, when necessary, the porous alumina layer 80b is further etched such that the pore diameter of the micropores 80p is further increased as shown in
To further increase the surface area of the porous alumina layer 80b, the aluminum film 80a may contain at least one impurity element selected from the group consisting of Fe, Si, Cu, Mn, Zn, Ni, Ti, Pb, Sn, and Mg. In this case, recessed portions which are difference from the micropores 80p are formed during the first etching cycle, so that the surface area of the porous alumina layer 80b can be further increased. Alternatively, recessed portions whose pore diameter is greater than that of the micropores 80p may be formed by carrying out the first etching cycle with an aluminum film being in contact with an electrode which contains a metal whose standard electrode potential is higher than that of the aluminum film.
In the above description, the porous alumina layer 80b itself is used as the mold 80, although the present invention is not limited to this example. The mold 80 may be manufactured by transfer of the porous alumina layer 80b. For example, the porous alumina layer 80b is transferred to a photocurable resin so as to form a mold which has a surface of a moth-eye structure, and this mold may be used as the mold 80 shown in
In the above description, the porous section 22 has raised portions which have a conical shape or a bell-like shape, although the present invention is not limited to this example. The porous section 22 may have raised portions which have a shape of a generally circular cylinder. In the above description which has previously provided with reference to
As described above, in applying and drying of the mixture A, the catalyst particles 14 move such that they are unevenly distributed so as to be present at the surface of the resin layer 12. Possible reasons that the catalyst particles 14 are unevenly distributed so as to be present at the surface of the resin layer 12 are: the surface free energy of the catalyst particles 14; the affinity of the catalyst particles 14 for the solvent; the incompatibility of the catalyst particles 14 with the resin; and phase separation of the thermoplastic resin. For example, when the surface free energy of the catalyst particles 14 is lower than those of the other constituents in the mixture, the catalyst particles 14 move from the inner part of the mixture toward the surface. When the catalyst particles 14 have affinity for the solvent in the mixture, the catalyst particles 14 move from the inner part of the mixture toward the surface along with evaporation of the solvent from the mixture. When the catalyst particles 14 exhibit incompatibility with the resin in the mixture, the catalyst particles 14 are forced to move from the inner part of the mixture toward the surface along with reduction of the content of the solvent in the mixture through drying, and forced movement of the catalyst particles 14 from the inner part of the mixture toward the surface is further enhanced by progress of phase separation of the thermoplastic resin.
As described above, a plurality of resins may be phase-separated. After application of the mixture, when cellular rotating convection occurs in the mixture during drying, a regular or periodic uneven shape is formed in the surface of the mixture. In general, the rotating convection occurs when a portion of the mixture near the surface is cooled by evaporation heat along with evaporation of the solvent and drying, and as a result, a temperature difference is caused between the upper part and the lower part of the mixture. Such convection is also called “Benard convection” or “Rayleigh-Benard convection”. In the convection which occurs in such a way, an upward movement and a downward movement are regularly repeated, and a regular or periodic uneven shape is arranged in the shape of cells across the mixture surface. The type of cellular rotating convection is not particularly limited but may be a different type of convection. For example, it may be Marangoni convection (density difference convection) which is attributed to a nonuniform distribution of the surface tension.
For example, in a mixture containing resin components which have phase separation properties from one another, these components may be allowed to undergo phase separation, whereby the catalyst particles 14 are moved. Detailed mechanisms of convection and phase separation are not yet explicated but can be inferred as described below.
In the case where convection is caused in the mixture which contains a plurality of phase-separated resins, firstly, convection cells occur after application. Then, phase separation occurs in each of the convection cells, so that the structure of the phase separation gigantically increases with the passage of time, and thereafter, growth of the phase separation stops at the cell wall of convection. As a result, an uneven shape is formed whose shape and height are controlled so as to have intervals according to the size and arrangement of the convection cells and controlled according to the phase separation structure. That is, a mixture is obtained whose shape, arrangement, and size are all controlled. It is thus inferred that, for the above reasons, the catalyst particles 14 are unevenly distributed so as to be present at the surface of the mixture A.
In the above description, in the case where anodization and etching are repeated to form the porous alumina layer 80b, the anodization and the etching may be repeatedly performed through a plurality of cycles till adjacent pores are partially connected to each other.
In this porous alumina layer 80b, adjacent pores are partially connected to each other. The average distance between the centers of adjacent pores is generally equal to the average value of the pore diameters of the pores. Note that, strictly speaking, the distance between the centers of adjacent pores is not constant, but the difference in distance between the centers of any two adjacent pores is relatively small.
This porous alumina layer 80b is formed by repeatedly performing anodization and etching through a plurality of cycles till adjacent pores are partially connected to each other. The thus-formed porous alumina layer 80b is used as the mold 80 (
Hereinafter, an example of the catalyst-supporting film 10 is described.
Here, the catalyst particles 14 used were inorganic oxide microparticles containing a crystalline titanium oxide and silica, on which zinc was supported. As these inorganic oxide microparticles, Atomy Ball (20NZT-AC) available from JGC Catalysts and Chemicals Ltd. was used. When the inorganic oxide microparticles containing a crystalline titanium oxide and silica are used, the dispersibility of the inorganic oxide microparticles is improved, and the stability of the mixture (dispersion) A is improved, while the adhesive property of a resultant film for the base is improved, as compared with a case where inorganic oxide microparticles containing only a crystalline titanium oxide are used.
These catalyst particles 14 were added to an acrylic resin. The inorganic oxide microparticles were 10 weight % with respect to the acrylic resin. This mixture A was applied to the base 30. The base 30 was a PET film.
As the mold 80, a porous alumina layer was provided which was formed by repeatedly performing anodization and etching on an aluminum film. The mixture A was irradiated with ultraviolet light from the base 30 side with the mold 80 being pressed against the mixture A. Thereafter, the mold 80 was separated from the base 30. The thus-formed catalyst-supporting film 10 provided on the base 30 was observed using a scanning electron microscope (SEM). The surface area of a region of the resin layer 12 which was not pressed with the mold (corresponding to
Further, the catalyst-supporting film 10 was placed over a glass plate such that the porous surface of the catalyst-supporting film 10 was exposed, and subjected to a light stability test. The test apparatus used was Super Xenon manufactured by Suga Test Instruments Co., Ltd. The irradiation condition was 60 W/m2 (wavelength: 300 nm to 400 nm). The irradiation duration was 250 hours. As a result, it was confirmed that there was substantially no deterioration in the catalyst-supporting film 10, and the catalyst-supporting film 10 can endure practical use.
In the above description, the porous section 22 of the catalyst-supporting film 10 has raised portions, and the supporting section 24 is continuous, but the present invention is not limited to this example. The supporting section 24 of the catalyst-supporting film 10 may have through holes.
The catalyst-supporting film 10 may be punched using a punching device which has a plurality of circular blades in a matrix arrangement as shown in
In the above description, the catalyst-supporting film 10 is provided on one of the two principal surfaces of the base 30, but the present invention is not limited to this example. The catalyst-supporting film 10 may be provided on each of the two principal surfaces of the base 30. In this case, using a relatively thin film, such as TAC, acrylic film, PET, or the like, as the base 30 is preferred.
As shown in
Catalyst-supporting films 10a, 10b may be formed on both sides of the thus-obtained base 30. Note that, in the case where a catalyst base 40 in which catalyst-supporting films 10a, 10b are provided on respective ones of the two principal surfaces of the base 30 is used for air cleaning (deodorization and decomposition of organic substances), arranging the catalyst base 40 so as to be parallel to the airflow direction as shown in
In recent years, air cleaning devices which utilize ions have been used in many places. However, such air cleaning devices can deactivate viruses and molds but cannot deactivate pollens which are greater than viruses and molds. The catalyst-supporting film 10 is also suitably used for air cleaning devices.
Hereinafter, an embodiment of an air cleaning device 50 of the present invention is described with reference to
The air cleaning device 50 of the present embodiment includes a catalyst-supporting film 10, an ion generating device 52, and a dust collection filter 54.
The ion generating device 52 generates a positive ion and a negative ion. The ion generating device 52 is, for example, a Plasmacluster ion (registered trademark) generating device which is manufactured by and commercially available from the applicant of the present application. The catalyst-supporting film 10 may be arranged in the form of a catalyst member 40 supported by the base 30. The dust collection filter 54 is preferably a HEPA filter. The HEPA filter is a type of air filter whose particle collection rate for particles of 0.3 μm in diameter at the rated flow rate is not less than 99.97% and whose initial pressure loss is not more than 245 Pa (Japanese Industrial Standards (JIS Standards)).
For example, air which is taken into the air cleaning device 50 is first supplied to the catalyst-supporting film 10. House dusts contained in the air are oxidatively degraded and deactivated by the catalyst-supporting film 10. The house dusts include pollens, spores, mites, mite droppings, and dead mite bodies. The diameter of cedar pollens is about 30 μm, and the diameters of pollens of other plants are approximately not less than 10 μm. Many of the other house dusts, such as mites, have sizes of not less than 2 μm and not more than 5 μm. The catalyst-supporting film 10 oxidatively degrades malodorous substances contained in the air to achieve deodorization.
Then, the Plasmacluster ion generating device 52 deactivates viruses and molds.
In the last, the dust collection filter 54 catches particles whose diameters are not more than 0.3 μm.
As described above, the air cleaning device 50 has not only a Plasmacluster ion generating function but also an oxidization function such that not only deactivation of viruses, and the like, but also deactivation of pollens and malodorous substances can be achieved. The catalyst-supporting film 10 is washable with water or alcohol, and therefore, maintenance of the catalyst-supporting film 10 is easy. Thus, the air cleaning device is applicable to a wider variety of uses.
The arrangement of the catalyst-supporting film 10 in the air cleaning device is not limited to the above-described example but may be appropriately varied according to the use or location of the air cleaning device. Further, the dust collection filter 54 may be omitted.
According to a catalyst-supporting porous film of the present invention, the catalytic action can be efficiently increased. Such a catalyst-supporting porous film is suitably used in an air cleaning device.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2011-020933 | Feb 2011 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP2012/051661 | 1/26/2012 | WO | 00 | 7/31/2013 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2012/105407 | 8/9/2012 | WO | A |
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| 20130315786 A1 | Nov 2013 | US |
