JP4776443B2 - Photocatalyst member - Google Patents

Description

  The present invention relates to a photocatalyst member having a photocatalyst function, and more particularly to a photocatalyst member having excellent friction fastness, particularly wiping resistance.

  In recent years, various photocatalytic members having a photocatalytic function formed by forming a photocatalytic layer on the surface of a base material made of ceramics, metal, synthetic resin or the like have been developed. Such photocatalyst members are used in coolers and vacuum cleaners to decompose bad odors, exhibit antibacterial / antifungal effects, and develop hydrophilicity by photocatalyst particles exposed on the surface. It is used for roofing materials for ports and soundproof boards for highways.

Further, a hydrophilic / lipophilic member is also proposed in which a layer containing photocatalyst particles is formed on the surface of the base material, and a hydrophilic portion and a lipophilic portion of about 10 to 100 nm are dispersed and formed in a mosaic pattern on the surface of this layer ( Patent Document 1).
Japanese Patent Laid-Open No. 10-166495

  However, when a thin and fragile photocatalyst layer is exposed on the surface like a conventional photocatalyst member, if the object hits or rubs, the photocatalyst layer may be damaged or peeled off by the impact force or frictional force. Thus, there is a problem that the photocatalytic function is lowered.

  Further, the hydrophilic / lipophilic member of Patent Document 1 forms a lipophilic surface by coordinating oxygen to the surface of the photocatalyst layer containing the photocatalyst particles, and emits light having a wavelength that excites the photocatalyst particles in the presence of water molecules. Irradiated to cause a coordinated oxygen cleavage reaction locally, and by this cleavage reaction, a hydroxyl group is bonded to a titanium atom, and a hydrophilic portion and a lipophilic portion of about 10 to 100 nm are dispersed and formed in a mosaic shape. Therefore, the photocatalyst layer itself is fragile and exposed on the surface in the same manner as the conventional photocatalyst member. Therefore, the hydrophilic / lipophilic member of Patent Document 1 also has a photocatalyst layer formed by external impact force or friction force. There has been a problem that the photocatalytic function is lowered due to damage or dropping off.

  The present invention has been made under the above circumstances, and an object of the present invention is to provide a photocatalyst member which is excellent in friction fastness, in particular, wiping resistance and hardly scratched.

To solve the above problems, engaging Ru photocatalytic member to the present invention is a photocatalyst member photocatalyst layer is laminated comprising photocatalyst particles on the substrate, the photocatalyst layer, the curable resin region photocatalytic layer is characterized in that the formed dispersed in implanted state such that the front surface flush.
And it is preferable that the thickness of this curable resin area | region is 10-500 nm.

In the photocatalyst member of the present invention, after irradiating light of 1 mW / cm ² with a black light blue lamp for 168 hours, the contact angle with water on the surface of the photocatalyst member on which the curable resin region is formed is 30. It is suitable that it is -90 degrees, and it is preferable that the ratio of the total area of all the curable resin area | regions which occupies for the area of the surface of a photocatalyst layer is 20-99%. Further, the curable resin region is preferably a region made of a thermosetting resin, and particularly preferably a region made of a melamine resin. And as a base material, the decorative board etc. which consist of the core material layer which consists of a fiber, a thermosetting resin, and an inorganic material, and the resin impregnated decorative layer laminated | stacked and integrated on it, etc. are used preferably, for example. In the photocatalyst member of the present invention, a protective layer may be formed between the base material and the photocatalyst layer, and an adhesive layer may be further formed between the base material and the protective layer.

Engaging Ru photocatalytic member in the present invention, the curable resin region formed by dispersing in embedded state to be flush with the surface of the photocatalyst layer, since the photocatalyst layer is protected, photocatalyst The friction fastness of the member, in particular, the wiping resistance is improved, and the scratch resistance is also improved. Accordingly, the photocatalyst particles are not easily peeled off from the substrate even when repeatedly rubbed, and the photocatalyst layer is hardly damaged even when hit by an object, so that a stable photocatalytic function can be exhibited over a long period of time. Strictly speaking, the surface between the curable resin regions of the photocatalyst layer is not protected, but since the distance between the curable resin regions is narrow, objects hit only the surfaces of the regions and damage each other. In other words, it is practically impossible that only the surfaces of the regions are wiped off and exfoliated, and therefore the friction fastness, particularly the wiping resistance and the scratch resistance are improved over the entire surface of the photocatalyst layer. It will be.

  And when the ratio of the total area of all the curable resin area | regions which occupies for the area of the surface of a photocatalyst layer is 20 to 99%, since the area between curable resin area | regions becomes small and a space | interval becomes narrow, the surface of a photocatalyst layer Overall friction fastness, especially wiping resistance and scratch resistance are improved. When the ratio of the total area of the curable resin region is less than 20%, the area protected by the curable resin region becomes too small, so that the friction fastness, particularly wiping resistance and scratch resistance are insufficient. If the ratio exceeds 99%, almost the entire surface of the photocatalyst layer is covered with the curable resin region, so that the malodorous and low molecular weight organic substance decomposition action, antibacterial / antifungal action, and the like are reduced.

  If the curable resin region is a region formed of a thermosetting resin, more preferably a melamine resin, the curable resin such as melamine resin is three-dimensionally cross-linked and cured to have high surface hardness and strength. In addition, since the frictional resistance of the surface is small, the improvement of the fastness to friction, particularly the wiping resistance and the improvement of the scratch resistance become more remarkable. And since the light transmittance of a curable resin area | region is high, visible light and an ultraviolet-ray can be permeate | transmitted well to a photocatalyst layer, and a photocatalyst function can fully be exhibited.

  It is not clear why the photocatalytic function is exerted even if a part or most of the surface of the photocatalyst layer is covered with the curable resin region formed by dispersion like the photocatalyst member of the present invention. Of course, the photocatalytic function is exhibited by the photocatalyst layer exposed between the curable resin regions, and since the thickness of the curable resin region is as thin as 10 to 500 nm, the photocatalyst of the photocatalyst layer is transmitted by the light transmitted through the curable resin region. Radical species and active oxygen species generated when the particles are activated scatter over the thin curable resin region to the surface side, decompose malodorous components and low molecular weight organic substances, antibacterial / antifungal properties, etc. It is presumed that this is done. It is also considered that one of the reasons is that malodorous components and low molecular weight organic substances on the surface pass through the thin curable resin region and are decomposed in contact with the photocatalyst layer.

  If the thickness of the curable resin region is thinner than 10 nm, the curable resin region is likely to be worn out and damaged, so that it is difficult to sufficiently improve the friction fastness, particularly the wiping resistance, and it is easy to be damaged. On the other hand, when it is thicker than 500 nm, it becomes difficult for substances involved in photocatalytic action such as radical species to diffuse to the surface side beyond the curable resin region, and low molecular weight organic substances pass through the curable resin region. Therefore, it is difficult to come into contact with the photocatalyst layer, so that the photocatalytic function is lowered, and the decomposition action of the malodorous component and the low molecular weight organic substance, the antibacterial / antifungal action and the like become insufficient.

  The above curable resin region is hard to be decomposed because the curable resin is cross-linked and cured in a three-dimensional network, so even if the photocatalytic action such as organic matter decomposition by the photocatalyst layer reaches the curable resin region The resistant resin region hardly deteriorates and can maintain excellent friction fastness, particularly wiping resistance and scratch resistance, over a long period of time.

  In addition, when the contact angle of the surface of the photocatalyst member with water is 30 to 90 ° as described above, the hydrophilicity is poor and the wettability of water is poor. Although it does not substantially exert its action, it can sufficiently exhibit the decomposition effects of malodorous components, low molecular weight organic substances, etc., and anti-bacterial and antifungal effects, and can cause decomposition of tobacco dust and cause sick house syndrome An effect such as decomposition of volatile organic compound (VOC) gas can be obtained. Furthermore, when the curable resin region is formed using an oil-repellent curable resin such as melamine resin, it is easy to wipe off oil stains even when used in an environment where oil is used, such as kitchens. Synergistically with the decomposition action, oil stain prevention effect can be exhibited.

  Further, as a base material, a decorative plate comprising a core layer made of glass fiber, carbon fiber, paper or the like, a thermosetting resin, and an inorganic material, and a resin-impregnated decorative layer laminated and integrated thereon. When used, the decorative board can be reduced in thermal expansion and contraction by the fibers of the core layer, so that a photocatalyst member that does not generate cracks in the photocatalyst layer and the curable resin region can be obtained. And it can be set as the makeup | decoration photocatalyst member which can visually observe the pattern and design of a resin impregnation decorative layer through a curable resin area | region and a photocatalyst layer. Further, since the decorative board can be easily made flame retardant or non-flammable, a flame retardant or non-flammable photocatalytic member can be obtained by using such a decorative board.

  Furthermore, when a protective layer is formed between the base material and the photocatalyst layer, the photocatalytic action of the photocatalyst layer is not exerted on the base material by the protective layer even when a base material made of a resin that is easily deteriorated by photocatalytic action is used. Since it is protected, deterioration of the substrate due to photocatalysis can be prevented. And what formed the adhesive layer between this protective layer and the base material, even when using a base material that cannot be directly bonded to the protective layer, the protective layer and the photocatalyst layer are cured by means such as lamination or transfer. The protective resin layer can be laminated on the base material at the same time, and the protective layer and the base material can be adhered to each other with the adhesive layer. Moreover, since the adhesive layer is protected by the protective layer, the adhesive layer is deteriorated by the photocatalytic action. There is nothing.

Hereinafter, specific embodiments and reference embodiments of the present invention will be described with reference to the drawings.

FIG. 1 is a cross-sectional view showing a photocatalyst member A of a reference form having a configuration different from that of the photocatalyst member according to the present invention only in that the curable resin region 4 protrudes from the surface of the photocatalyst layer 3 .

The photocatalyst member A is formed by laminating a protective layer 2 and a photocatalyst layer 3 in this order on the surface of one side of the base material 1, and forming a small curable resin region 4 having a regular or irregular shape on the surface of the photocatalyst layer 3. 3 is a plate-like member formed by being dispersed in a state protruding from the surface of 3. In the photocatalyst member A of this reference form , the protective layer 2, the photocatalyst layer 3, and the curable resin region 4 are formed on one side of the base material 1. The protective layer 2 may be omitted when the material 1 is hardly altered or deteriorated by the photocatalytic action.

  The substrate 1 may be formed of any material such as a synthetic resin (such as a thermoplastic resin or a curable resin), glass, cement, an inorganic material, stone, ceramic, or metal. As the thermoplastic resin, a polyester resin such as polycarbonate or polyethylene terephthalate, an acrylic resin, a vinyl chloride resin, a polyolefin resin, a styrene resin, or a single or mixed or copolymer resin is used. Curing resins include acrylic resins, melamine resins, phenolic resins, diallyl phthalate resins, and unsaturated polyester resins that are cured by irradiation with heat, ultraviolet rays, electron beams, and the like, and addition of polymerization initiators and catalysts. Resins, urethane resins, epoxy resins, silicone resins and the like are used. Alternatively, these resins can be used in combination. Furthermore, as the base material 1, these resins are combined with inorganic fibers such as glass fibers, organic fibers such as carbon fibers and paper, and inorganic fillers, or the above fibers are cored with these resins. Composite materials, and fiber reinforced cosmetics are also used.

  Among the base materials 1 made of the above-mentioned various materials, the light-transmitting resin, for example, the base material 1 made of polycarbonate resin has excellent transparency and impact resistance, so that it has a photocatalytic function. It is preferably used as the base material 1 of a photocatalyst member A for building materials such as materials, carports, road soundproofing plates, and waistboards or road materials. The thickness and shape of the base material 1 made of such a polycarbonate resin are not particularly limited. However, in the case of the photocatalytic member A used for the above roofing material, carport, waist plate, etc., the thickness is 0.5 to 4 mm. A flat plate-like, corrugated plate-like, or folded half-shaped substrate 1 is preferably used. In the case of the photocatalytic member A used for a road soundproof plate, a flat plate-like substrate 1 having a thickness of 4 to 10 mm is suitably used. Used. And the base material 1 which further provided the heat ray absorbing function, the heat ray reflecting function, the weather resistance function, the electromagnetic wave absorbing function, the electromagnetic wave reflecting function, the antistatic function, the hard coat function and the like is also preferably used.

  In addition, the base material 1 made of a composite material blended with the above glass fiber or inorganic filler, or the base material 1 made of a fiber-reinforced decorative material has a small thermal expansion and contraction because it contains fibers and inorganic fillers. Therefore, the photocatalyst layer 2 is preferably used because it does not thermally expand and contract to generate cracks. These base materials 1 have sufficient intensity | strength that the thickness is about 1-10 mm.

  The protective layer 2 serves to protect the substrate 1 by preventing the photocatalytic action of the photocatalyst layer 3 from reaching the substrate 1. Preferred examples of the protective layer 2 include a composition obtained by uniformly mixing an inorganic substance such as silica and a binder resin such as a silicone resin such as polydimethylsiloxane, an acrylic resin, or a fluororesin, or a silicone resin and an acrylic resin. An inorganic-organic layer formed of a composition comprising an inorganic substance and an organic substance such as a mixture or a copolymer resin, a layer formed of a silicone resin, or a metal oxide such as amorphous titanium oxide A layer etc. can be mentioned.

    The protective layer 2 is preferably formed to have a thickness of 0.1 to 10 μm. When the thickness is less than 0.1 μm, it is difficult to effectively block the photocatalytic action, and the photocatalytic action reaches the base material 1 and the base material 1. Inconvenience that deteriorates. On the other hand, even if it is thicker than 10 μm, no further improvement in the photocatalytic action-blocking effect is observed, resulting in wasted material. A more preferable thickness of the protective layer 2 is 0.5 to 5 μm.

  The protective layer 2 is not necessarily formed when the substrate 1 is made of glass, cement, inorganic material, stone, ceramics, metal, or the like that does not deteriorate due to photocatalytic action.

  The photocatalyst layer 3 is a layer formed by uniformly dispersing photocatalyst particles, silica or silicone resin, and, if necessary, 1% by mass or less of a dispersant or binder, and the photocatalyst contained therein The particles perform photocatalytic actions such as decomposing malodorous components and low molecular weight organic substances, exhibiting antibacterial and antifungal effects, and developing hydrophilicity. However, since this photocatalyst member A is difficult to be made hydrophilic due to the dispersion of the curable resin region having poor hydrophilicity on the surface of the photocatalyst layer 3, it does not exhibit a self-purifying effect due to the hydrophilicity. .

As the photocatalyst particles dispersed in the photocatalyst layer 3, any of particles activated by ultraviolet rays and particles activated by visible light can be used. As the former ultraviolet-activated particles, for example, metal oxides such as titanium oxide, zinc oxide, tin oxide, SrTiO ₃ and WO ₃ are used. Among them, titanium oxide, particularly anatase titanium oxide, is most preferably used because it has a high photocatalytic function and is easily available.

  Examples of the latter visible light activated particles include photocatalyst particles obtained by doping the above metal oxide particles with nitrogen, fluorine, sulfur, carbon, or the like, or platinum-supported, oxygen-deficient, brookite-type photocatalyst particles. Is used. Although the mechanism by which these photocatalyst particles exhibit the photocatalytic function by visible light is not clear, for example, in the case of photocatalyst particles in which titanium oxide is doped with nitrogen, Ti—N or Ti—O—N chemical bonds are not present. It is considered that the photocatalytic function is exhibited by absorbing visible light. Among these visible light activated particles, photocatalyst particles in which titanium oxide, particularly anatase-type titanium oxide is doped with nitrogen, have higher activity than other particles and are easily available. Is used preferably because it exhibits a high photocatalytic function.

  Further, inorganic materials such as apatite, zeolite, silica (silicon dioxide), alumina, zinc oxide, magnesium oxide, titanium oxide, zirconium phosphate, zirconia, magnesia, and calcia are added to the above-mentioned ultraviolet ray activated particles or visible light activated particles. Reticulated coated photocatalyst particles obtained by coating a mesh with a mesh or porous structure are also preferably used. The inorganic material has a thickness of several angstroms to several μm and is coated on the photocatalyst particles so as to be 0.1 to 5.0% by mass, and the diameter of the reticulated coated photocatalyst particles is 500 μm or less, preferably 50 μm or less. More preferably, the thickness is 0.001 to 20 μm. Such a net-coated photocatalyst particle exhibits a photocatalytic function when ultraviolet rays and / or visible light reach the photocatalyst particle through the coating network. Among the above-mentioned network-coated photocatalyst particles, the photocatalyst particles coated with titanium oxide with a porous material of zeolite or silica capture the malodorous component by zeolite or silica, and decompose the malodorous component by the photocatalytic action of titanium oxide. The decomposition effect of malodorous components is remarkable and is extremely preferable.

  The photocatalyst particles described above are preferably dispersed uniformly in the photocatalyst layer 3 and contained in an amount of 5 to 99% by mass. If it is less than 5% by mass, it becomes difficult to exert the photocatalytic function, and if it is contained in an amount of more than 99% by mass, the photocatalyst layer becomes brittle and it becomes difficult to form the layer. The more preferable content of the photocatalyst particles is 5 to 50% by mass when the ultraviolet-activated photocatalyst particles are contained, 5 to 99% by mass when the visible-light activated photocatalyst particles are contained, When it is contained, it is 5 to 80% by mass.

  As the silica to be contained in the photocatalyst layer 3 together with the photocatalyst particles, an inorganic material mainly composed of silica such as a silica precursor or water glass is used. Further, the photocatalyst layer 3 may be formed by containing a silicone resin together with the photocatalyst particles instead of the silica, or the photocatalyst layer 3 may be formed by containing a mixture of silica and silicone resin together with the photocatalyst particles. . These silica, silicone resin, and a mixture of both are contained in the photocatalyst layer 3 in an amount of 95 to 1% by mass.

  Since the light passing through the curable resin region 4 and reaching the photocatalyst layer 3 has a small amount of energy, the photocatalyst layer 3 must contain an amount of photocatalyst particles that can exhibit the photocatalytic function with the small amount of energy. For this, the thickness of the photocatalyst layer 3 is preferably 5 to 300 nm. If the thickness is less than 5 nm, the amount of the photocatalyst particles becomes insufficient and it becomes difficult to exert the photocatalytic function. Further, even if the thickness is greater than 300 nm, no further improvement in the photocatalytic function is observed, and rather, while using for a long period of time. There is a disadvantage that cracks occur in the photocatalyst layer 3. If the material is used in an environment where sufficient light for activating the photocatalyst such as ultraviolet rays can be obtained, the thickness of the photocatalyst layer 3 can be set as thin as 5 to 35 nm. However, in a use environment where sufficient light cannot be expected, the photocatalyst layer If the thickness of 3 is set to 35 to 300 nm, preferably 50 to 200 nm, and the content of the photocatalyst particles is not increased, it is difficult to exert the photocatalytic function.

  When the base material 1 is made of a synthetic resin having a large thermal expansion and contraction, particularly a thermoplastic synthetic resin, the photocatalytic layer 3 tends to expand and contract with the thermal expansion and contraction of the base material 1, and a certain level of stress is applied to the photocatalytic layer 3. However, when the thickness of the photocatalyst layer 3 is 5 to 35 nm as described above, the internal stress associated with expansion and contraction is reduced, so that the generation of cracks can be prevented. If cracks occur when the photocatalyst member A is transparent or colored, the initial appearance such as transparency and hue cannot be maintained due to light scattering, but the photocatalyst layer 3 has the above thickness. If cracks are prevented from occurring, the initial transparency and hue can be maintained.

  On the other hand, the base material 1 is a decorative plate described later composed of a core layer made of inorganic fiber, organic fiber, thermosetting resin, and inorganic material and a resin-impregnated decorative layer, or glass fiber mixed with synthetic resin. In the case of a base material having a small thermal expansion and contraction such as a fiber reinforced composite material or a resin-impregnated fiber composite material in which a fiber is impregnated with a synthetic resin, the photocatalyst layer 3 has a thickness of 300 nm. Cracks do not occur even if the thickness is too large.

  From the above, in an environment where light that activates a photocatalyst such as ultraviolet rays can be obtained abundantly in the photocatalyst particles, when the base material 1 is a base material having a large thermal expansion and contraction such as a thermoplastic resin, It is preferable to set the thickness to 5 to 35 nm. On the other hand, in an environment in which light such as ultraviolet rays for activating the photocatalyst cannot be sufficiently obtained, the base material 1 is impregnated with the above decorative board, fiber reinforced composite material, or resin impregnation. In the case of a base material having a small thermal expansion and contraction such as a fiber composite material, it is understood that the thickness of the photocatalyst layer 3 is preferably set to 35 to 300 nm.

  The curable resin region 4 is a region made of a synthetic resin that is cured by heat, light, electron beam, moisture, catalyst, polymerization initiator, etc., and has a high surface hardness friction obtained by crosslinking and curing the resin in a three-dimensional network. It has robustness. Since the curable resin region 4 needs to transmit light and reach the photocatalyst layer 3, it needs to have transparency or translucency, and is particularly preferably transparent. Specific curable resins include melamine resins, phenol resins, diallyl phthalate resins, acrylic resins, epoxy resins, polyimide resins, unsaturated polyester resins, urethane resins, silicone resins, and the like. Alternatively, a mixed or copolymer resin is used, and among these, thermosetting resins such as thermosetting acrylic resins, thermosetting melamine resins, thermosetting phenol resins having good transparency and high surface hardness are used. Preferably used. In addition, thermosetting melamine resins and thermosetting phenolic resins are used. Especially, thermosetting melamine resins that have high binding energy and are not easily decomposed into photocatalysts and that have high surface hardness and excellent transparency are very preferably used. Is done. A urethane acrylate resin having a self-healing property against scratches is also preferably used.

  This curable resin region needs to be able to exhibit the photocatalytic function of the photocatalyst layer 3 on the surface side beyond the region, so that the thickness is preferably 500 nm or less. When it is thicker than 500 nm, even if the photocatalytic action of the photocatalytic layer 3 is strong, the photocatalytic action is not sufficiently exhibited on the surface side of the curable resin region. On the other hand, if the curable resin region becomes too thin, the friction fastness, in particular, the wiping resistance decreases, and the strength and scratch resistance of the curable resin region also decrease, so it is possible to ensure a thickness of at least 10 nm. preferable. Therefore, the thickness of the curable resin region is preferably set to 10 to 500 nm, and more preferably set to a thickness of 20 to 200 nm in order to suppress the decrease in photocatalytic action as much as possible. Further, it is more preferable that the thickness is 35 to 200 nm. The photocatalytic action of the photocatalyst layer 3 is always exerted on the curable resin region. However, since the curable resin region is difficult to be decomposed by crosslinking and curing the resin in a three-dimensional network as described above, There will be no deterioration or deterioration within a short period of time.

From the microscopic viewpoint, the contact angle between the surface of the photocatalyst member and water seems to be strictly different between the curable resin region 4 and the exposed portion of the photocatalyst layer 3 between the regions. The contact angle with water on any part of the surface of the photocatalyst member is substantially the same, and the light of 1 mW / cm ² is irradiated for 168 hours using a black light blue lamp. When the surface contact angle with water is measured, the surface contact angle is preferably 30 to 90 °. If the contact angle is at this level, the self-purifying effect due to hydrophilicity, which is one of the photocatalytic actions, will not be exhibited, but the decomposition action, antibacterial and antifungal action of malodorous components and low molecular weight organic substances, etc. should be sufficiently exerted. Can do. In addition, since the photocatalytic action is not so strong when the contact angle is at this level, the curable resin layer 4 can be formed even after a long period of time, coupled with the fact that the curable resin region is not easily decomposed as described above. There is almost no risk of deterioration or deterioration.

  The shape of the curable resin region may be indefinite or fixed, and the area of each region may be small or large, but the total area of all the curable resin regions in the surface area of the photocatalyst layer 3 Is preferably in the range of 20 to 99%. If the ratio of the total area of the curable resin region is less than 20%, the area protected by the curable resin region becomes too small, so that the friction fastness, particularly the wiping resistance and the scratch resistance become insufficient. When the ratio of the curable resin region is larger than 75%, the appearance may be impaired, and therefore the preferable ratio of the total area of the curable resin region is 25 to 75%.

  The dispersion form of the curable resin region 4 is not particularly limited. For example, the curable resin regions may be scattered on the surface of the photocatalyst layer 3 in a state where the curable resin regions are individually separated. It may be dispersed on the surface of the photocatalyst layer 3 in a state of being connected to each other, or both of these dispersion states may be mixed, but in any of the dispersed forms, the curable resin region of the photocatalyst layer 3 It must be distributed substantially uniformly over the entire surface.

Since the area of the curable resin region varies depending on the dispersion state, it is not particularly limited. However, the curable resin region in an individually separated state has an area of about 1.0 × 10 ^{−4 to} 0.1 mm ^2. It is preferable that the curable resin region is easily peeled off by friction when the size is smaller than 1.0 × 10 ⁻⁴ mm ² , and the photocatalytic performance, particularly the organic matter resolution is hindered when the size is larger than 0.1 mm ^2. Inconveniences such as degradation and antibacterial / antifungal effects are reduced.

  Further, when the methylene blue decomposition test described in the description of the examples described later was conducted to decompose the malodorous components and low molecular weight organic substances on the surface of the photocatalyst member A, or to exhibit antibacterial / antifungal properties, The activity index R is 4.2 to 5.0 [nmol / l / min], and can exhibit a sufficient effect.

  The photocatalyst member A has an antistatic function, a conductive function, a heat ray reflecting function, a heat ray absorbing function, an electromagnetic wave absorbing function, an electromagnetic wave reflecting function, a hard coat function, an antioxidant function, a water repellent function, a water repellent function, as necessary. An oil function, a self-healing function for scratches, and the like may be imparted. Moreover, when the above-mentioned visible light activation particles are included as the photocatalyst particles of the photocatalyst layer 3, the ultraviolet ray absorbent may be included in the curable resin region to the extent that the photocatalytic action is not hindered to provide a weather resistance function. Good.

  Such a photocatalytic member A can be manufactured, for example, by the following method.

  One method is to previously mix and disperse a liquid curable resin (for example, a liquid melamine resin) and a coating for a protective layer (for example, a paint in which silica and a binder resin are mixed and dispersed, a polysiloxane and an acrylic resin). Paint, a paint mainly composed of a copolymer resin of a silicone resin and an acrylic resin, etc.), a paint for a photocatalyst layer (for example, photocatalyst particles, silica or silicone resin, and if necessary, 1% by mass or less A coating material in which a dispersing agent is mixed and dispersed in a solvent or water is prepared. Then, using a method such as dip coating, spray coating, spin coating, roll coating, bar coating, etc., a protective layer coating is applied to the surface of the substrate 1 and dried to form the protective layer 2, and a photocatalyst is formed thereon. After forming the photocatalyst layer 3 by coating and drying the layer coating, a curable resin region 4 is formed by spraying and curing a liquid curable resin on the surface of the photocatalyst layer 3 using a spray coater or the like. Thus, the photocatalytic member A is obtained.

  Another method is to previously apply the photocatalyst layer paint on a release film and dry it to form the photocatalyst layer 3, and then apply the protective layer paint onto the release film and then dry the protective layer. 2 is formed to produce a transfer film. Then, this transfer film is laminated on the base material 1 (for example, a thermoplastic resin plate) so that the protective layer 2 is on the base material 1 side and integrated by thermocompression bonding by hot pressing, and then the release film is removed. This is a method of obtaining the photocatalyst member A by forming a curable resin region 4 by spraying a liquid curable resin on the surface of the photocatalyst layer 3 using a spray coater or the like and then curing it.

  The photocatalyst member A having the above-described configuration can be subjected to thermal bending or bending at room temperature when the substrate 1 is, for example, a thermoplastic resin plate, and remains plate-like or bent. After being processed, it is used as the above-mentioned building material or road material, or used as an interior member of an electric appliance such as an air purifier, a cooler or a refrigerator. When natural light, illumination light, or irradiation light hits the photocatalyst layer 3, the photocatalyst particles are activated and the photocatalytic action is exerted on the exposed surface of the photocatalyst layer 3 between the curable resin regions. Beyond that, it is also exerted on the surface side, and it has the effect of decomposing malodorous components, low molecular weight organic substances, etc., and antibacterial and antifungal effects. Moreover, since part or most of the photocatalyst layer 3 is covered and protected by the curable resin region 4, the photocatalyst layer 3 is protected even if the surface is repeatedly wiped or hit. There is almost no exfoliation or damage, and a good photocatalytic function can be exhibited over a long period of time.

FIG. 2 is a cross-sectional view showing a photocatalyst member B of another reference form having a configuration different from that of the photocatalyst member according to the present invention only in that the curable resin region 4 protrudes from the surface of the photocatalyst layer 3 .

  In this photocatalyst member B, an adhesive layer 5 is further formed between the substrate 1 and the protective layer 2. The adhesive layer 5 includes a base material 1 and a protective layer 2 among adhesive resins such as urethane resin, acrylic resin, polyvinyl alcohol resin, vinyl acetate resin, thermoplastic epoxy resin, and silicone resin. It is preferable to select and form a material that adheres well to both. The thickness of the adhesive layer 5 is preferably about 0.1 to 50 μm. If the thickness is less than 0.1 μm, the adhesive strength may be poor and may peel off. Since no further improvement is observed, the material is wasted. A more preferable thickness of the adhesive layer 5 is 1 to 10 μm.

  Since the configuration of the photocatalyst member B other than the adhesive layer is the same as that of the photocatalyst member A described above, the description thereof is omitted.

  Such a photocatalyst member B is manufactured by the following method, for example. That is, a film made of an adhesive resin such as an acrylic resin is prepared, and the protective layer paint and the photocatalyst layer paint used in the production of the photocatalyst member A are sequentially applied to the adhesive resin film and dried. Then, a laminate film having the protective layer 2 and the photocatalyst layer 3 formed thereon is prepared. Then, this laminate film is superposed on the base material 1 and bonded and integrated by hot pressing, and a liquid curable resin is sprayed on the photocatalyst layer 3 using a spray coater or the like and then cured to be curable resin. When the region 4 is formed, the photocatalytic member B is obtained.

In addition, an adhesive resin paint, a protective layer paint, and a photocatalyst layer paint are applied and dried in this order on the base material, and an adhesive layer 5, a protective layer 2, and a photocatalyst layer 3 are laminated and further formed. Of course, the photocatalyst member B may be manufactured by spraying a liquid curable resin on the surface of the photocatalyst layer 3 and then curing it to form the curable resin region 4.
In addition, a transfer film in which the photocatalyst layer coating material, the protective layer coating material, and the adhesive resin coating material are applied and dried in this order is produced and transferred to the base material. After forming, the release film is removed, and a liquid curable resin is sprayed on the surface of the photocatalyst layer 3 using a spray coater or the like, followed by curing to form the curable resin region 4. .

  Such a photocatalyst member B also has the same effect as the photocatalyst member A described above. And even when the base material 1 and the protective layer 2 cannot be directly joined, they can be bonded and integrated so as not to peel off through the adhesive layer 5.

FIG. 3 is a sectional view showing a photocatalyst member C of still another reference embodiment having a configuration different from that of the photocatalyst member according to the present invention only in that the curable resin region 4 protrudes from the surface of the photocatalyst layer 3 .

  This photocatalyst member C includes, as a base material 1, a fiber layer made of inorganic fibers or organic fibers, a core material layer 1a made of a thermosetting resin and an inorganic material, and a resin-impregnated decorative layer 1b laminated thereon. Using a decorative board 10, the adhesive layer 5, the protective layer 2, and the photocatalyst layer 3 are laminated on the surface, and the curable resin region 4 is projected and dispersed on the surface of the photocatalyst layer 3. It is a member.

  As the decorative board 10, for example, glass fibers are impregnated with a thermosetting resin such as a thermosetting melamine resin or a thermosetting phenol resin, and an inorganic material such as aluminum hydroxide, magnesium hydroxide, calcium carbonate, or talc is used. The core material layer 1a is formed so as to contain 95 to 80% by mass of the whole, and a thermosetting resin such as a thermosetting melamine resin or the like on a decorative paper containing titanium oxide on the surface of the core material layer 1a. A laminate of the resin-impregnated decorative layer 1b impregnated so as to be 60 to 150% by mass is preferably used. As described above, when the inorganic material of the core material layer 1a and the thermosetting resin amount of the resin-impregnated decorative layer 1b are within the above ranges, the flame-retardant or non-combustible decorative board 10 can be obtained.

  In addition, since the protective layer 2, the photocatalyst layer 3, the curable resin area | region 4, and the adhesive bond layer 5 are the same as those of the photocatalyst member A or the photocatalyst member B mentioned above, description is abbreviate | omitted.

  Such a photocatalyst member C is manufactured by the following method, for example. That is, the photocatalyst layer coating material is applied onto a release film and dried to form the photocatalyst layer 3, and the protective layer coating material is applied thereon and dried to form the protective layer 2, and further bonded. A transfer film is prepared by applying an adhesive layer coating obtained by dissolving an adhesive resin in a solvent and drying to form an adhesive layer 5. On the other hand, the core layer 1a and the resin-impregnated decorative layer 1b are superposed and hot pressed to produce a decorative board 10. Then, the transfer film is superposed on the surface of the decorative plate 10 so that the adhesive layer 5 of the transfer film overlaps and is heat-pressed and joined and integrated. Then, the release film is removed, and a spray coater or the like is placed on the photocatalyst layer 3. The photocatalytic member C is obtained when the liquid curable resin is sprayed and then cured to form the curable resin region 4.

  When the decorative board 10 is manufactured by the above manufacturing method, the transfer film is superposed on the uncured resin-impregnated decorative layer 1b so that the adhesive layer 5 of the transfer film is overlaid. The impregnating resin of the decorative board 10 is cured by pressing, and at the same time, the resin-impregnated decorative layer 1b and the protective layer 2 are joined, and then the release film is removed, and a liquid coater is applied on the photocatalyst layer 3 using a spray coater or the like. The photocatalyst member C can be obtained even when the curable resin region 4 is formed by spraying the curable resin and then curing. Therefore, in this manufacturing method, if the protective layer 2 is bonded to the resin-impregnated decorative layer 1b by the uncured resin of the resin-impregnated decorative layer 1b, the adhesive layer 5 can be omitted.

In addition, after apply | coating an adhesive resin coating material, the coating material for protective layers, and the coating material for photocatalyst layers in this order on the decorative board 10, and drying, it is liquid hardening using a spray coater etc. on the photocatalyst layer 3. After spraying the photosensitive resin, it is cured to form the curable resin region 4, or after applying and drying the protective layer coating and the photocatalyst layer coating in this order, the spray coater is applied onto the photocatalyst layer 3. It is needless to say that the photocatalyst member C may be manufactured by spraying a liquid curable resin using the above and then curing to form the curable resin region 4.
Further, an adhesive resin paint, a protective layer paint, and a photocatalyst layer paint are applied and dried in this order, integrated by hot pressing, and then cured on the photocatalyst layer 3 to be curable. The photocatalytic member C may be manufactured by forming the resin region 4.

  The photocatalytic member C obtained by the above method is easy to make the decorative board 10 as the base material 1 flame-retardant or non-flammable, and the curable resin region 4 on the surface is also a layer of a highly heat-resistant melamine resin. Therefore, it becomes a flame-retardant or non-flammable photocatalyst member, and the pattern and design of the resin-impregnated decorative layer 1b can be visually observed through the curable resin region 4 and the photocatalyst layer 3, so that it is suitably used as a building material such as an interior material. The Then, like the photocatalyst members A and B described above, the photocatalytic action of the photocatalyst layer 3 reaches the surface of the member C, and the functions of decomposition of malodorous components and the like, antibacterial and antifungal functions are exhibited, and the photocatalyst layer 3 Since the coating is partially or mostly protected, even if wiping and cleaning are repeated or an object hits, the photocatalyst layer 3 is not peeled off or damaged, and a good photocatalytic action can be maintained over a long period of time.

FIG. 4 is a sectional view showing an embodiment of the photocatalytic member according to the present invention.

This photocatalyst member D is the above-mentioned photocatalyst member except that the curable resin region 4 is dispersed and formed in a state of being embedded in the photocatalyst layer 3 so as to be flush with the surface of the photocatalyst layer 3. The configuration is the same as C. Thus, even when the curable resin region 4 is embedded flush, frictional force or impact force acts on the surface of the curable resin region 4 and is received, and the photocatalyst layer 3 between the regions is exposed to the exposed surface. Since the frictional force and impact force do not act strongly, the photocatalyst layer 3 is not exfoliated or damaged even when repeated wiping or hitting an object, and a good photocatalytic action can be maintained over a long period of time. The decorative plate 10, the core layer 1a, the resin-impregnated decorative layer 1b, the protective layer 2, the photocatalyst layer 3, the curable resin region 4, and the adhesive layer 5 that are the base material 1 are all the same as described above. Therefore, explanation is omitted.

  Such a photocatalyst member D is manufactured by the following method, for example. That is, after spraying a liquid curable resin on the release film using the spray coater or the like, it is cured to form the curable resin resin region 4, and the photocatalyst layer coating material is formed thereon. The transfer film is produced by applying the coating for protective layer and the adhesive resin coating in this order and drying to form the photocatalyst layer 3, the protective layer 2, and the adhesive layer 5. Then, after the transfer film is overlapped so that the adhesive layer 5 is in contact with the surface of the decorative plate 10 and thermocompression integrated by hot press, the photocatalyst member D can be obtained by removing the release film. Also in this case, it goes without saying that the base material may be formed of any material such as the above-mentioned synthetic resin, glass, cement, inorganic material, stone, ceramic, metal, etc. instead of the decorative board 10.

Further, by pressing the above-described photocatalyst member A, photocatalyst member B, or photocatalyst member C, the photocatalyst member D can be obtained even if the curable resin region is embedded in the photocatalyst layer 3 in a flush manner.

  In this photocatalyst member D, when the decorative board 10 is produced, the transfer film is superposed on the uncured resin-impregnated decorative layer 1b so that the adhesive layer 5 of the transfer film is in contact with the transfer film. The resin impregnated on the decorative board 10 may be cured by hot pressing, and at the same time, the resin-impregnated decorative layer 1b and the adhesive layer 5 may be bonded together, and then the release film may be removed. If the protective layer 2 is bonded to the resin-impregnated decorative layer 1b by the uncured resin of the layer 1b, the adhesive layer 5 can be omitted.

  The above photocatalyst members A, B, C, and D are all formed in a flat plate shape (including a plate shape, a sheet shape, and a film shape), but the present invention is not limited to a flat plate photocatalyst member. For example, a pipe or a rod is used as the base material 1, and the layers 2, 3, 5 and the curable resin region 4 are formed on the outer peripheral surface thereof, or the layers 2, 3 are provided on the surface of the three-dimensional solid base material 1. , 5 and a curable resin region 4 formed on the photocatalyst member having a desired shape.

  Next, more specific examples of the present invention will be described.

[Example 1]
As a base material, a glass fiber is impregnated with a thermosetting melamine resin and an inorganic hydroxide such as aluminum hydroxide and calcium carbonate is contained, and a core material layer sheet and titanium oxide-containing decorative paper are used as a thermosetting melamine resin. And a resin-impregnated decorative layer sheet impregnated with.

  On the other hand, a paint in which polydimethylsiloxane and an acrylic resin are uniformly mixed is prepared as a protective layer paint. As a photocatalyst layer paint, 4% by mass of visible light responsive photocatalytic titanium oxide doped with nitrogen, and 0. A coating material in which 5% by mass was uniformly dispersed with an alcohol-based dispersion was prepared. Moreover, the thermosetting melamine resin liquid for forming the curable resin area | region 4 was also prepared.

  And after spreading the above-mentioned thermosetting melamine resin liquid on the surface of the release film made of polyethylene terephthalate with a spray coater (Anest Iwata Airbrush Highline HP-BH, nozzle diameter 0.2 mm), curing Then, the curable resin region 4 is partially formed so as to have a thickness of 100 nm, and the photocatalyst layer coating material is applied thereon and dried to dry the photocatalyst layer having a thickness of 100 nm (the thickness of the photocatalyst layer). Indicates a thickness not including the thickness of the melamine resin region, and the same shall apply hereinafter), and the above protective layer coating material is applied thereon and dried to provide a protective layer having a thickness of 3.0 μm. By forming, a transfer film was produced.

The uncured core material layer sheet and the uncured resin-impregnated decorative layer sheet are stacked, and the transfer film is stacked on top so that the protective layer side is in contact with the uncured resin-impregnated decorative layer sheet. The thermosetting melamine resin between the core material layer sheet and the resin impregnated decorative layer sheet is cured by thermocompression bonding for 15 minutes under the conditions of a temperature of 140 ° C. and a pressure of 80 kgf / cm ² . At the same time, the resin-impregnated decorative layer sheet and the protective layer of the transfer film are joined, and then removed from the press molding machine and the release film is removed, so that the protective layer, photocatalyst layer, and photocatalyst layer are formed on the surface of the decorative plate. A flat photocatalyst member was produced in which a part of the curable resin region embedded so as to be flush with the surface was laminated and integrated in this order.

About the obtained photocatalyst member, when the ratio of the total area of the curable resin area | region occupied to the surface of a photocatalyst layer was measured with the following method, the curable resin area | region occupied 33% of the surface of the photocatalyst layer.
FIG. 5 shows a screen after binarization processing in the following method. As can be seen from FIG. 5, it was found that light black portions due to the silver nitrate reaction were scattered in spots, and only partially reacted. As a result, it can be seen that the curable resin region exists only in a part of the photocatalyst layer.

(Test method)
A 0.1N silver nitrate aqueous solution is placed in a container, the photocatalyst member obtained is immersed in the silver nitrate aqueous solution, and 0.5 ± 0.05 mW from a black light blue (BLB) lamp disposed above the photocatalyst member. UV light was irradiated for 30 minutes at an output of / cm ² . This is because the portion where the curable resin region exists on the photocatalyst layer does not exhibit a light black color due to the silver nitrate reaction in a short time even if the photocatalyst member is irradiated with ultraviolet rays in an aqueous silver nitrate solution, and the curable resin region on the photocatalyst layer The portion where no is present utilizes the property of promptly showing a light black color by the silver nitrate reaction. After UV irradiation, the photocatalyst member is taken out from the silver nitrate aqueous solution, observed and photographed at 450 times using a Keyence Digital HF Microscope VH-8000, and the photograph is binary using a Keyence Picture Folder. After the conversion, the area of the light black portion was digitally calculated.
The ratio of the total area of all the curable resin regions in the surface of the photocatalyst layer was calculated by dividing the total area colored in light black by the area in the range in which the light black colored portion was calculated. .

Further, the obtained photocatalyst member was irradiated with ultraviolet rays of 1 ± 0.05 mW / cm ² for 168 hours with a black light blue (BLB) lamp. At regular intervals, 20 ml of ion-exchanged water is dropped onto the curable resin layer on the surface using a microsyringe, and the contact angle of the water droplets on the surface is measured by an image processing contact angle meter (Kyowa Interface Science Co., Ltd., CA-A). ) Were measured at three points by the three-point method, and the average value was obtained. As a result, the contact angle was 83 ° before irradiation, but after 24 hours, 48 hours, 72 hours, 120 hours, and 168 hours, 82 °, 81 °, 81 °, 80 °, It was 78 °.

  Further, when the obtained photocatalyst member was examined for organic matter decomposability by conducting the following methylene blue decomposition test, the decomposition activity index R was 4.5 [nmol / l / min], and the photocatalyst layer was cured by melamine. Although it was partially covered with the conductive resin region, it was confirmed that a good decomposition action was exhibited.

(Methylene blue decomposition test)
The photocatalyst member is cut to a size of 60 mm square to prepare three test pieces. A cylindrical cell is liquid-tightly attached to each test piece with silicone grease, and a methylene blue adsorbent (methylene blue) is attached to each cell. 35 ml of a solution obtained by dissolving trihydrate in purified water so as to have a concentration of 0.02 mmol / l) is injected, covered with a cover glass, and adsorbed with methylene blue until adsorption saturation is achieved. Then, the methylene blue adsorbed liquid in the cell was replaced with 0.01 mmol of a new methylene blue test liquid, and each test piece was irradiated with ultraviolet rays of 1 ± 0.05 mW / cm ² for 20 minutes from directly above. The absorption spectrum in the wavelength range of 600 to 700 nm is measured with a spectrophotometer, and the liquid used for the measurement is immediately returned to the cell and again irradiated with ultraviolet rays. The operation of irradiating ultraviolet rays for 20 minutes in this procedure and measuring the absorption spectrum is repeated nine times until the total irradiation time reaches 3 hours. Then, the decomposition activity index is obtained by the following procedure.
That is, the absorbance Abs (t) at the peak top of the absorption spectrum after irradiation for ultraviolet t minutes is read (t = 20, 40, 60, 80, 100, 120, 140, 160, 180), and the peak top of the initial absorption spectrum is read. The absorbance at is read and this is defined as Abs (0). Then, using Abs (0), a conversion coefficient K for converting the absorbance into the concentration is obtained from the following formula (1), and using this conversion coefficient K, the absorbance Abs is obtained from the following formula (2). (T) is converted to methylene blue test solution concentration C (t) [μmol / l] after t minutes, and as shown in FIG. 4, C (t) [μmol / l] is plotted on the vertical axis, and the horizontal axis is plotted on the horizontal axis. Take the UV irradiation time (minutes) and plot the data for each of the three specimens. Then, the slope calculated for each specimen (the most inclination is linearly approximated by the least square method to choose four points greater inclination) and a _{n (n} = 1, 2, 3), by the following equation (3) The decomposition activity index R is obtained.
K = 10 [μmol / l] / Abs (0) Formula (1)

C (t) = K × Abs (t) [μmol / l] (2)

R = | (a ₁ + a ₂ + a ₃ ) / 3 | × 10 ³ [nmol / l /] Formula (3)

  Further, when the wiping resistance of the three test pieces prepared by cutting the obtained photocatalyst member was examined by the following method, the entire surface of the test piece was colored with silver nitrate even in the initial period when it was not wiped. Even when the number of wipings was 500 times or 3000 times, the entire surface of the test piece showed a color reaction of silver nitrate. From this, it was found that even when the photocatalyst layer was covered with the melamine curable resin region, the photocatalytic action was exhibited on the surface of the photocatalyst member. And it turned out that the photocatalyst layer coat | covered with the melamine curable resin area | region is not worn out and exfoliated even if it wipes 3000 times.

(Wiping resistance test)
Friction tester for dyeing fastness test (JIS L 0823) was improved to flat plate, weight (200g) and white cotton cloth for friction Kanaki No. 3 (JIS L 0862) were attached to this tester, and test piece was 500 times And wipe 3000 times. Then, each test piece was immersed in a 0.1N silver nitrate solution and irradiated with ultraviolet light of 1 ± 0.05 mW / cm ² for 10 hours with a black light blue lamp, and the presence or absence of silver deposition on the surface of each test piece ( The presence or absence of the photocatalyst layer of the test piece is determined by the presence or absence of a color reaction of silver nitrate.

[Example 2]
As a base material, a glass fiber is impregnated with a thermosetting melamine resin, and a core layer containing aluminum hydroxide and calcium carbonate as inorganic materials, and a thermosetting melamine resin on a decorative paper containing titanium oxide. A decorative board was prepared by laminating and integrating the impregnated resin-impregnated decorative layer with a hot press.

  A urethane adhesive Nipponporan 2301 manufactured by Nippon Polyurethane Industry Co., Ltd. was prepared as an adhesive layer coating material. In addition, the same protective layer coating material, photocatalyst layer coating material, and thermosetting melamine resin solution as in Example 1 were prepared.

  And, on the surface of the release film made of polyethylene terephthalate, the above thermosetting melamine resin liquid is sprayed and cured by a spray coater to form a curable resin region having a thickness of 100 nm, on which the above-mentioned The photocatalyst layer coating was applied and dried to form a 100 nm thick photocatalyst layer, and the above protective layer coating was further applied and dried to form a 3.0 μm thick protective layer, and Furthermore, the above-mentioned adhesive coating material was applied thereon and dried to form an adhesive layer having a thickness of 5.0 μm, thereby producing a transfer film.

This transfer film was placed on a decorative plate so that the adhesive layer was superimposed on the resin-impregnated decorative layer of the decorative plate, and set in a press molding machine under the conditions of a temperature of 140 ° C. and a pressure of 10 kgf / cm ² . Bonded the decorative board and transfer film by thermocompression for 3 minutes, and then removed from the press molding machine and removed the release film, so that the adhesive layer, protective layer, photocatalyst layer, photocatalyst on the surface of the decorative board A flat photocatalyst member was produced in which the curable resin regions embedded so as to be flush with the surface of the layer were laminated and integrated in this order.

  About the obtained photocatalyst member, when the ratio of the total area of the curable resin area | region occupied to the surface of a photocatalyst layer was measured by the same method as Example 1, the curable resin area | region occupied 62% of the surface of the photocatalyst layer. .

  Further, after the obtained photocatalyst member was irradiated with ultraviolet light for 168 hours with a black light blue (BLB) lamp in the same manner as in Example 1, the contact angle of water was measured by the same method as that used in Example 1. . As a result, the contact angle, which was 85 ° before irradiation, became 80 ° after irradiation for 168 hours, indicating no hydrophilicity.

  Further, when the obtained photocatalyst member was examined for organic matter decomposability by the same method as in Example 1, the decomposition activity index R was 4.2 [nmol / l / min], and the photocatalyst layer was in the melamine resin region. Although it was coated, it was confirmed that the surface of the photocatalyst member exhibits a good decomposition action.

  In addition, when the wiping resistance of three test pieces prepared by cutting the obtained photocatalyst member was examined, all the surfaces of the test piece exhibited a color reaction of silver nitrate even in the initial stage where no wiping was performed. Even when the number of times reached 3000, all the surfaces of the test piece exhibited a color reaction of silver nitrate. From this, it was found that even the photocatalyst member obtained by this production method exhibited a photocatalytic action on its surface. And it turned out that the photocatalyst layer coat | covered with the melamine curable resin area | region is not worn out and exfoliated even if it wipes 3000 times.

[ Reference example ]
As the substrate, the same decorative board as in Example 2 was prepared.

  Furthermore, the same adhesive layer coating material, protective layer coating material, photocatalyst layer coating material, and thermosetting melamine resin solution as those in Example 2 were prepared.

  Then, the adhesive layer paint is applied on the decorative plate and dried to form an adhesive layer having a thickness of 0.5 μm, and the protective layer paint is applied thereon and dried to obtain a thickness. A protective layer having a thickness of 3.0 μm is formed, and the photocatalyst layer coating material is applied thereon and dried to form a photocatalyst layer having a thickness of 100 nm. Further, the thermosetting melamine resin liquid is applied thereon. Curing that protrudes from the surface of the adhesive layer, protective layer, photocatalyst layer, and photocatalyst layer on the surface of the decorative board by spraying and curing with a spray coater to form a curable resin region having a thickness of 100 nm A flat photocatalyst member in which the conductive resin region was laminated and integrated in this order was produced.

  About the obtained photocatalyst member, when the ratio of the total area of the curable resin area | region occupied to the surface of a photocatalyst layer was measured by the same method as Example 1, the curable resin area | region occupied 30% of the surface of the photocatalyst layer. .

  Further, after irradiating the photocatalyst layer through the curable resin region of the obtained photocatalyst member with a black light blue (BLB) lamp for 168 hours in the same manner as in Example 1, water was obtained by the same method as that used in Example 1. The contact angle of was measured. As a result, the contact angle, which was 81 ° before irradiation, became 75 ° after irradiation for 168 hours, which was lower than that of Example 1 and Example 2, but did not decrease to the contact angle having a self-cleaning action. .

  Furthermore, when the obtained photocatalyst member was examined for organic matter decomposability in the same manner as in Example 1, the decomposition activity index R was 5.0 [nmol / l / min].

  The three test pieces prepared by cutting the obtained photocatalyst member were examined for wiping resistance. Even in the initial stage where no wiping was performed, all the surfaces of the test piece showed a color reaction of silver nitrate, and the number of wiping operations was Even after reaching 3000 times, all the surfaces of the test piece exhibited a color reaction of silver nitrate.

[Comparative Example 1]
Instead of the transfer film prepared in Example 2, a transfer film was prepared by laminating a photocatalyst layer having a thickness of 100 nm, a protective layer having a thickness of 3.0 μm, and an adhesive layer having a thickness of 5.0 μm on the surface of the release film. A photocatalyst member of Comparative Example 1 (without a curable resin layer on the surface) was produced in the same manner as in Example 2 except that an adhesive layer, a protective layer, and a photocatalyst layer were laminated and integrated on the surface of the decorative board.

About this photocatalyst member, it carried out similarly to Example 1, and investigated the contact angle with water, a decomposition activity index, and wiping resistance. As a result, the contact angle with water was 60 ° before irradiation, but it became 10 ° at the stage of irradiation for 24 hours and decreased to 4 ° after irradiation for 48 hours. The photocatalysts of Examples 1 and 2 and Reference Example It was more hydrophilic than the member. The decomposition activity index was 6.5 [nmol / l / min], which was larger than those of the photocatalyst members of Examples 1 and 2 and the reference example . This is presumably because the photocatalytic action is exerted more strongly than the photocatalyst members of Examples 1 and 2 and the reference example because the photocatalyst layer of the photocatalyst member of Comparative Example 1 is exposed on the entire surface. Moreover, all the test pieces of the photocatalyst member of Comparative Example 1 had no silver nitrate color reaction when wiped 500 times, and the photocatalyst layer was already worn out and exfoliated, and the wiping resistance was poor. .

The results of Examples 1 and 2 and Reference Example and Comparative Example 1 are summarized in Table 1, and a graph of the contact angle between Example 1 and Comparative Example 1 is shown in FIG. The change is shown in FIG.

In Examples 1 and 2 and Reference Example having a curable resin region, the contact angle with water when irradiated with ultraviolet rays for 168 hours is much larger than that of Comparative Example 1 and does not exhibit hydrophilicity. Although the decomposition activity index is lower than that of Comparative Example 1, the organic catalyst exhibits a good organic substance decomposition action even though the photocatalyst layer is partially or mostly covered with the curable resin region. Yes. Since the photocatalyst layer is partially or mostly covered with the curable resin region, it exhibits high wiping resistance, and the photocatalyst layer does not wear out or peel off, and can stably decompose organic substances over a long period of time. It is possible to play.

It is a sectional view showing a photocatalytic member according to a reference embodiment. It is a sectional view showing a photocatalytic member according to another reference embodiment. Further is a sectional view showing a photocatalytic member according to another reference embodiment. It is sectional drawing which shows one Embodiment of the photocatalyst member which concerns on this invention. It is the photograph which image | photographed what immersed the sample of Example 1 in the silver nitrate aqueous solution, and irradiated the ultraviolet-ray with the black light blue lamp, and binarized the picked-up photograph. It is the graph which showed the relationship between the contact angle (degree) of the water of Example 1 and Comparative Example 1 and ultraviolet irradiation time (hours). The data obtained in the methylene blue decomposition test of Example 1 and Comparative Example 1 is plotted, and is a graph showing the relationship between the methylene blue test solution concentration C (t) [μmol / l] and the ultraviolet irradiation time (min). is there.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Base material 1a Core material layer 1b Resin impregnation decorative layer 2 Protective layer 3 Photocatalyst layer 4 Curable resin area | region 5 Adhesive layer A, B, C, D Photocatalyst member

Claims (9)

  A photocatalyst member in which a photocatalyst layer containing photocatalyst particles is laminated on a substrate, and dispersed in this photocatalyst layer in a state where the curable resin region is flush with the surface of the photocatalyst layer. A photocatalyst member characterized by being formed. 2. The photocatalytic member according to claim 1 , wherein the thickness of the curable resin region is 10 to 500 nm. The photocatalyst member according to claim 1 or 2 , wherein the contact angle with water is 30 to 90 ° after irradiating light of 1 mW / cm ² with black light blue for 168 hours. The photocatalyst member according to any one of claims 1 to 3 , wherein a ratio of the total area of all the curable resin regions to the surface area of the photocatalyst layer is 20 to 99%. The photocatalyst member according to any one of claims 1 to 4 , wherein the curable resin region is a region made of a thermosetting resin. The photocatalyst member according to any one of claims 1 to 5 , wherein the curable resin region is a region made of a melamine resin. Substrate, a core layer more the fibers and the thermosetting resin and inorganic, claims 1 and more becomes decorative plate and integrally laminated resin impregnated decorative layer thereon claim 6 The photocatalyst member described in 1. The photocatalyst member according to any one of claims 1 to 7 , wherein a protective layer is formed between the substrate and the photocatalyst layer. The photocatalyst member according to claim 8 , wherein an adhesive layer is formed between the substrate and the protective layer.

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