JP4695553B2 - 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 formed on the surface like a conventional photocatalyst member, when the object hits or rubs, the photocatalyst layer is 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 formed on the surface in the same manner as a 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 circumstances described above, and provides a photocatalyst member that is excellent in friction fastness, in particular, wiping resistance and is not easily damaged, and a method for producing the photocatalyst member. Yes.

  In order to solve the above-mentioned problems, a photocatalyst member according to the present invention comprises a photocatalyst layer containing photocatalyst particles via a protective layer on a base material made of a thermosetting resin or a base material containing a thermosetting resin. And a photocatalyst member in which the thermosetting resin is scattered in an exposed state on the surface of the photocatalyst layer, and at least a part of the exposed and scattered thermosetting resin passes through the photocatalyst layer and the protective layer. It is characterized by being continuous.

  Another photocatalyst member according to the present invention has a photocatalyst layer containing photocatalyst particles laminated on a base material made of a thermosetting resin or a base material containing a thermosetting resin via a protective layer, and A photocatalyst member in which a thermosetting resin is scattered in an exposed state on the surface of the photocatalyst layer, and at least a part of the exposed thermosetting resin passes from the base material through the protective layer and the photocatalyst layer to the surface of the photocatalyst layer It is characterized by having shifted to.

In each photocatalyst member of the present invention, the thickness of the protective layer is 0.3 to 5.0 μm, and the ratio of the total area of the exposed portion of the thermosetting resin to the surface area of the photocatalyst layer is The contact angle with water on the surface after irradiation with light of 1 mW / cm ² intensity for 168 hours using black light blue is preferably 30 to 90 °. In addition, as a base material, a decorative board in which a thermosetting resin-impregnated decorative layer is laminated and integrated on a core layer made of fibers, a thermosetting resin, and an inorganic material is preferably used. A thermosetting melamine resin is preferably used.

  On the other hand, in the method for producing a photocatalyst member according to the present invention, a photocatalyst layer containing photocatalyst particles and a protective layer are sequentially formed on a release film to produce a transfer film, and an uncured thermosetting resin is contained. Overlaying the transfer film on the substrate forming material so that the protective layer is on the substrate side and thermocompression bonding allows the uncured thermosetting resin to pass from the substrate forming material through the protective layer and the photocatalyst layer. Transfer to the surface of the photocatalyst layer and expose and scatter on the surface of the photocatalyst layer, and transfer the protective layer and the photocatalyst layer onto the substrate formed by thermosetting the uncured thermosetting resin. It is a feature.

  As in the photocatalyst member according to the present invention, a photocatalyst layer is laminated on a substrate via a protective layer, and a thermosetting resin is scattered in an exposed state on the surface of the photocatalyst layer, and the exposed and scattered thermosetting When at least a part of the resin is continuous to the substrate through the photocatalyst layer and the protective layer, the photocatalyst layer is protected by the exposed exposed portions of the thermosetting resin. The wiping resistance is improved and the scratch resistance is also improved. Moreover, since the exposed portion of the thermosetting resin exposed on the surface of the photocatalyst layer is supported by the thermosetting resin continuous from the base material to the surface of the photocatalyst layer, the strength against external impact force and friction force Is large and exhibits excellent protective action. Therefore, even if the surface of the photocatalyst member is repeatedly rubbed, the photocatalyst layer and the photocatalyst particles are difficult to exfoliate, and the photocatalyst layer is difficult to be damaged even when hit by an object, so that a stable photocatalytic action can be exhibited over a long period of time. . Strictly speaking, the surface of the photocatalyst layer between the exposed portions of the thermosetting resin is not directly protected, but since the distance between the exposed portions of the thermosetting resin is narrow, the photocatalyst layer between the exposed portions is short. In reality, there is absolutely no case where only the surface hits and damages, or only the surface of the photocatalyst layer between the exposed parts is wiped off and the photocatalyst particles are exfoliated, and therefore, the entire surface of the photocatalyst member is covered. Friction fastness, especially wiping resistance and scratch resistance are improved.

  Like other photocatalyst members according to the present invention, a photocatalyst layer containing photocatalyst particles is laminated on a base material made of a thermosetting resin or a base material containing a thermosetting resin via a protective layer. In addition, the thermosetting resin is scattered in an exposed state on the surface of the photocatalyst layer, and at least a part of the exposed thermosetting resin moves from the base material to the surface of the photocatalyst layer through the protective layer and the photocatalyst layer. In this case, since the photocatalyst layer is protected by the exposed portions where the thermosetting resin is scattered, the friction fastness of the photocatalyst member, in particular, the wiping resistance is improved, and the scratch resistance is also improved. Moreover, since the exposed portion of the thermosetting resin exposed on the surface of the photocatalyst layer is supported by the thermosetting resin present in the transition path from the base material to the surface of the photocatalyst layer, High strength against impact force and friction force from the surface, and exhibits excellent protective action. Therefore, even if the surface of the photocatalyst member is repeatedly rubbed, the photocatalyst layer and the photocatalyst particles are difficult to exfoliate, and the photocatalyst layer is difficult to be damaged even when hit by an object, so that a stable photocatalytic action can be exhibited over a long period of time. .

  Although it is not clear why the photocatalytic action is exerted even when the thermosetting resin is exposed in a scattered state on the surface of the photocatalyst layer as in the photocatalyst member of the present invention, exposure of the photocatalytic layer to the thermosetting resin is not clear. In addition to the photocatalytic action exerted between the parts, the radical species and active oxygen species generated by the activation of the photocatalyst particles of the photocatalyst layer by the light transmitted through the exposed portion of the thermosetting resin are also thermoset. This is presumably because it is scattered to the surface side of the exposed portion of the photosensitive resin and performs a photocatalytic action such as a decomposition action of malodorous components and low molecular weight organic substances and an antibacterial / antifungal action.

  In the photocatalyst member according to the present invention, as described above, at least a part of the thermosetting resin continues to the base material through the photocatalyst layer and the protective layer, or from the base material through the protective layer and the photocatalyst layer. When the production method of transferring the protective layer and the photocatalyst layer to the surface of the base material to be described later by thermocompression and laminating them is used, the base material is thermally cured by the pressure. This is presumed to be because some of the thermosetting resin transfer passages are blocked by fluctuations in the protective layer and / or the photocatalyst layer after the photopolymer passes through the protective layer and the photocatalyst layer to the surface of the photocatalyst layer. The

  The photocatalytic member having a protective layer thickness of 0.3 to 5.0 μm is easy to form a thermosetting resin continuous up to the base material, and the amount of the thermosetting resin that migrates (exudes) to the surface of the photocatalytic layer. Therefore, the ratio of the exposed portion of the thermosetting resin on the surface of the photocatalyst layer and the state where the exposed portion is scattered can be improved, and the photocatalytic layer surface can be dispersed without reducing the photocatalytic action. Friction fastness, particularly wiping resistance and scratch resistance can be greatly improved. When the thickness of the protective layer is less than 0.3 μm, the resin permeability of the protective layer is too good, the amount of the thermosetting resin exposed on the surface of the photocatalyst layer becomes too large, or it migrates to the surface of the photocatalyst layer (exudation) ) The amount of the thermosetting resin is too large, the appearance of the photocatalytic member is lowered, and the photocatalytic action may be lowered. On the other hand, when the thickness of the protective layer exceeds 5.0 μm, the resin permeability of the protective layer is significantly reduced, and the amount of the thermosetting resin exposed on the surface of the photocatalyst layer becomes too small or moves to the surface of the photocatalyst layer. Since the amount of the thermosetting resin to be drastically reduced and it becomes difficult to be exposed on the surface of the photocatalyst layer, it is difficult to improve the friction fastness and scratch resistance of the surface of the photocatalyst layer.

  In the photocatalyst member in which the ratio of the total area of the exposed portions of the thermosetting resin to the surface area of the photocatalyst layer is 20 to 99%, the area and interval between the exposed portions of the thermosetting resin are appropriately small. As a result, the friction fastness of the entire surface of the photocatalyst layer, in particular, the wiping resistance and the scratch resistance are further improved. If the ratio of the total area of the exposed portion of the thermosetting resin is less than 20%, the protective action of the surface of the photocatalyst layer by the exposed portion of the thermosetting resin is reduced, so that frictional fastness, particularly wiping resistance and scratch resistance are prevented. If the ratio is more than 99%, the appearance of the photocatalyst member will be deteriorated, and it will lead to degradation of malodorous components and low molecular weight organic substances, photocatalytic action such as antibacterial and antifungal action, etc. Fear arises.

Further, the photocatalytic member having a contact angle with water of 30 to 90 ° after irradiating light of 1 mW / cm ² with black light blue for 168 hours has poor hydrophilicity and water wettability. Because it is bad, the self-purification effect due to hydrophilicity, which is one of the photocatalytic actions, is not substantially exhibited, but the photocatalytic action such as the decomposition action of malodorous components and low molecular weight organic substances and the antibacterial / antifungal action is sufficiently exerted. It is also possible to obtain effects such as decomposition of tobacco crabs and decomposition of volatile organic compound (VOC) gas that causes sick house syndrome.

  A photocatalyst member using a decorative board in which a thermosetting resin-impregnated decorative layer is laminated and integrated on a core material layer made of fibers, a thermosetting resin, and an inorganic material as a base material is a core material of the decorative board. Thermal expansion and contraction can be suppressed by the fibers of the layer, so that cracks can be prevented from occurring in the photocatalyst layer and the protective layer, and the pattern and design of the thermosetting resin-impregnated decorative layer can be passed through the photocatalyst layer and the protective layer. It can also be set as the visible photocatalyst member. In addition, since the decorative board can be easily made flame-retardant or non-flammable, the use of such a decorative board makes it possible to provide a flame-retardant or non-flammable photocatalytic member.

  A photocatalytic member in which the thermosetting resin that is exposed on the surface of the thermosetting resin or the photocatalyst layer is a thermosetting melamine resin has a high surface hardness when the melamine resin is cross-linked and cured three-dimensionally. In addition, since the surface frictional resistance is small, the fastness to friction on the surface of the photocatalyst layer, in particular, the improvement in wiping resistance and the improvement in scratch resistance become remarkable. In addition, thermosetting melamine resin has high light transmittance, and even if it is exposed on the surface of the photocatalyst layer, it transmits visible light and ultraviolet rays well and activates the photocatalyst particles of the photocatalyst layer, so it fully exhibits the photocatalytic action. Can be made. In addition, since the thermosetting melamine resin is an oil-repellent resin, the photocatalytic member in which such an oil-repellent melamine resin is scattered in an exposed state on the surface of the photocatalyst layer is used in an environment such as a kitchen where oil is frequently used. When used, oil stains can be easily wiped off, and an excellent oil stain prevention effect can be exhibited in synergy with the organic matter decomposition action by the photocatalyst layer.

  Such a photocatalyst member can be efficiently mass-produced by the production method of the present invention described above.

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

  FIG. 1 is a schematic cross-sectional view showing an embodiment of a photocatalyst member according to the present invention, and FIG. 2 is a schematic cross-sectional view showing another embodiment of the photocatalyst member according to the present invention.

  The photocatalyst members A1 and A2 shown in FIG. 1 and FIG. 2, respectively, have a photocatalyst layer 3 containing photocatalyst particles on a sheet-like or plate-like base material 1 made of a thermosetting resin with a protective layer 2 interposed therebetween. It is laminated, and the thermosetting resin 4 is scattered in an exposed state on the surface of the photocatalyst layer 3 to form an exposed portion 4a, thereby improving the friction fastness and scratch resistance of the photocatalyst layer 3. . And at least a part of the exposed portion 4a of the thermosetting resin scattered and exposed is continuously connected from the exposed portion 4a to the base material 1 through the photocatalyst layer 3, or the base material 1 To the exposed portion 4a on the surface of the photocatalyst layer through the protective layer 2 and the photocatalyst layer 3, and connected (hereinafter referred to as a connected thermosetting resin 4 when these connected thermosetting resins are collectively referred to). ing.

  The difference in configuration between the photocatalyst member A1 and the photocatalyst member A2 is that the photocatalyst member A2 has a slightly larger amount of the linked thermosetting resin 4 than the photocatalyst member A1, so that the linked thermosetting of the photocatalyst member A2 is performed. As shown in FIG. 2, the exposed portion 4a of the curable resin 4 expands to the periphery, and the area is larger than the exposed portion 4a of the coupled thermosetting resin 4 of the photocatalyst member A1. Other configurations are common to the photocatalyst member A1 and the photocatalyst member A2.

  In addition, although these photocatalyst members A1 and A2 both have laminated | stacked the protective layer 2 and the photocatalyst layer 3 on the single side | surface of the base material 1, of course, you may form on both surfaces of the base material 1. FIG. Moreover, although the connection thermosetting resin 4 is connected linearly and continuously in the drawing, the connection thermosetting resin 4 is not limited thereto, and may be continuous in a curved line. Thus, it is generally formed.

  When these photocatalyst members A1 and A2 are manufactured using a transfer manufacturing method to be described later, all the exposed portions of the thermosetting resin are theoretically continuous with the substrate 1 as shown in FIGS. Although most of the exposed portions of the thermosetting resin are continuous with the base material 1 and the rest are discontinuous with the base material 1 (in FIG. 1 and FIG. Not shown). In this way, a part of the exposed portion of the thermosetting resin is discontinuous with the base material 1 when the protective layer 2 and the photocatalyst layer 3 are transferred onto the surface of the base material 1 by thermocompression bonding and laminated. After the thermosetting resin of the base material 1 is exposed to the surface of the photocatalyst layer 3 through the protective layer 2 and the photocatalyst layer 3 due to the pressure, the protective layer 2 fluctuates due to a rolling action or the like due to the pressure. This is presumed to be because a part of the thermosetting resin transition passage is blocked. Further, when the exposed portion 4a of the connected thermoplastic resin 4 is enlarged as shown in FIG. 2, a part of the enlarged exposed portion 4a is divided and dispersed on the surface of the photocatalyst layer 3 as one cause. It is estimated that.

  As the base material 1, what consists of thermosetting resin, what mix | blended inorganic fiber (for example, glass fiber etc.), organic fiber (for example, carbon fiber, cellulose fiber, etc.), an inorganic filler, etc. in thermosetting resin, inorganic or An organic fiber aggregate impregnated with a thermosetting resin, a fiber-reinforced decorative material described later containing the thermosetting resin, or the like is used. A base made of a base material in which fibers, inorganic fillers, etc. are blended with the above thermosetting resin, a base material in which a fiber assembly is impregnated with a thermosetting resin, or a fiber-reinforced decorative material containing a thermosetting resin The material is preferably used because thermal expansion and contraction is suppressed by the fiber and the inorganic filler, and the protective layer 2 and the photocatalyst layer 3 are not cracked.

  The substrate 1 may be colorless and transparent, colored and transparent, colored and opaque, or may have a pattern or pattern so as to suit the use of the photocatalytic members A1 and A2. The thickness and shape of the photocatalyst members A1 and A2 are not particularly limited. Further, the base material 1 may be appropriately provided with a heat ray absorbing function, a heat ray reflecting function, a weather resistance function, an electromagnetic wave absorbing function, an electromagnetic wave reflecting function, an antistatic function, a hard coat function, and the like.

  The thermosetting resin constituting the substrate 1 and the thermosetting resin contained in the substrate 1 are exposed to the surface continuously or transferred to the surface of the photocatalyst layer 3, and the exposed portion 4 a of the photocatalyst layer 3 is exposed. Because it is scattered on the surface and improves the friction fastness and scratch resistance of the photocatalyst layer 3, it is crosslinked and cured in a three-dimensional network during heat curing, and exhibits high strength, melamine resin, phenol resin, diallyl phthalate A resin, an acrylic resin, an epoxy resin, a polyimide resin, an unsaturated polyester resin, a urethane resin, a silicone resin or the like may be used alone or as a mixture or copolymer resin. Among these, thermosetting acrylic resin, melamine resin, phenol resin, etc. with good transparency and high surface hardness are preferably used. Especially, the binding energy is high, it is difficult to be decomposed by photocatalysis, and the surface hardness is high. A melamine resin excellent in transparency is very preferably used. In addition, urethane acrylate resin having self-healing ability against scratches is also preferably used.

  The protective layer 2 serves to protect the base material 1 by preventing the photocatalytic action of the photocatalyst layer 3 from reaching the base material 1. Preferred examples of the protective layer 2 include inorganic substances such as silica and the like. , A layer formed of a composition in which a silicone resin such as polydimethylsiloxane, a binder resin such as an acrylic resin or a fluororesin is uniformly mixed, or a mixed resin or copolymer resin of a silicone resin and an acrylic resin. Examples thereof include a layer, a layer formed of only a silicone resin, and a layer formed of a metal oxide such as amorphous titanium oxide.

  The thickness of the protective layer 2 is important in controlling the amount of the thermosetting resin exposed and scattered on the surface of the photocatalyst layer 3, and an appropriate amount of the thermosetting resin 4 is exposed on the surface of the photocatalyst layer 3. In order to improve the fastness to friction, particularly the wiping resistance and the scratch resistance, the thickness of the protective layer 2 is preferably set in the range of 0.3 to 5.0 μm. If the thickness of the protective layer 2 is less than 0.3 μm, the resin permeability of the protective layer 2 is too good and the amount of the thermosetting resin that is exposed and scattered on the surface of the photocatalyst layer 3 becomes too large. 3 is covered with a large amount of exposed thermosetting resin so that the appearance of the photocatalytic members A1 and A2 deteriorates, and the photocatalytic action of the photocatalytic layer 3 may be reduced. On the other hand, if the thickness of the protective layer 2 exceeds 5.0 μm, the resin permeability of the protective layer 2 is significantly reduced, and the amount of the thermosetting resin exposed on the surface of the photocatalyst layer 3 is drastically reduced, so that the photocatalyst layer 3 Therefore, it is difficult to improve the friction fastness and scratch resistance of the surface of the photocatalyst layer 3. A more preferable thickness of the protective layer 2 is 0.5 to 2.0 μm.

  Further, even if the crosslinking density of the resin contained in the protective layer 2 is controlled, the amount of the thermosetting resin 4 exposed on the surface of the photocatalyst layer 3 can be controlled. That is, when the crosslink density is increased, the resin permeability is decreased and the thermosetting resin exposed and scattered on the surface of the photocatalyst layer 3 is decreased. When the crosslink density is decreased, the resin permeability is improved and the photocatalyst layer 3 The amount of thermosetting resin exposed and scattered on the surface increases. Therefore, if the crosslinking density becomes too high, the thermosetting resin exposed and scattered on the surface of the photocatalyst layer is drastically reduced, so that it is difficult to improve the friction fastness and scratch resistance of the surface of the photocatalyst layer 3. If the density is too low, a large amount of thermosetting resin may be exposed and scattered, resulting in a decrease in the appearance of the photocatalyst members A1 and A2 and a decrease in the photocatalytic action of the photocatalyst layer 3, and adhesion to the substrate 1. It is important to properly control the crosslinking density because the force decreases and peeling and whitening occur.

  For example, when the protective layer 2 is made of an acrylic-silicone copolymer resin, the crosslinking density can be controlled by adjusting the amount of the modified silicone group such as an alkoxysilyl group as the reactive group, or by adjusting the type and amount of the curing agent. It can be done by adjusting or adjusting the amount of heat (heating temperature x time) for drying the protective layer when forming a transfer film by forming a photocatalyst layer and a protective layer on the release film as described later it can.

  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, the photocatalyst members A1 and A2 are hydrophilic because the thermosetting resin 4 having poor hydrophilicity is exposed on the surface of the photocatalyst layer 3 and the exposed portions 4a are dispersed. There is no self-purification effect due to crystallization.

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 is difficult to exert a photocatalytic action, and if it is contained in an amount of more than 99% by mass, the photocatalyst layer 3 becomes brittle and it is difficult to form a 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.

  The photocatalyst layer 3 has an amount of photocatalyst that can exert a sufficient photocatalytic action by the energy of light directly irradiated and the energy of light irradiated to the adjacent photocatalyst layer 3 through the exposed portion 4a of the thermosetting resin 4. It is necessary to contain particles, and for that purpose, the thickness of the photocatalyst layer 3 is preferably set in the range of 5 to 300 nm. If the thickness is less than 5 nm, the amount of photocatalyst particles becomes insufficient, and it becomes difficult to exert photocatalytic action. Even if the thickness is greater than 300 nm, no further improvement in photocatalysis is observed. There is a disadvantage that cracks occur in the photocatalyst layer 3. In the case of a photocatalyst member used in an environment where light for activating photocatalyst particles such as ultraviolet rays can be sufficiently obtained, the photocatalytic action can be exerted even if the thickness of the photocatalyst layer 3 is set as thin as 5 to 35 nm. In the case of a photocatalyst member used in an environment where no photocatalysis can be expected, the photocatalyst layer 3 is set to a thickness of 35 to 300 nm, preferably 50 to 200 nm, and the photocatalyst action is sufficiently exhibited unless the photocatalyst particle content is increased. It becomes difficult to do.

  For example, when the base material 1 is made of a thermosetting resin having a large thermal expansion and contraction, 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. When it occurs, cracks are generated. 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 generation of cracks can be prevented. If cracks occur in the photocatalyst layer 3 when the substrate 1 is transparent or colored, it becomes cloudy due to light scattering and cannot maintain the initial appearance such as transparency and hue. By preventing the occurrence of cracks by increasing the thickness, it becomes possible to maintain the initial transparency and hue.

  In contrast, the base material 1 includes a base material in which fibers, inorganic fillers, and the like are blended in a thermosetting resin, a base material in which a fiber assembly is impregnated with a thermosetting resin, and a thermosetting resin. In the case of a base material having a small thermal expansion and contraction, such as a base material made of a fiber-reinforced decorative material, which will be described later, the photocatalyst layer 3 has a thickness of 300 nm because the expansion and contraction of the photocatalyst layer 3 accompanying the thermal expansion and contraction of the base material 1 is small. Even so, cracks do not occur.

  From the above, a photocatalyst member used in an environment in which light such as ultraviolet rays for activating the photocatalyst particles can be sufficiently obtained and using the substrate 1 having a large thermal expansion and contraction ensures the photocatalytic action, cracks From the viewpoint of preventing the photocatalyst, it is preferable to set the thickness of the photocatalyst layer 3 to 5 to 35 nm. On the other hand, the photocatalyst member is used in an environment where light such as ultraviolet rays for activating the photocatalyst cannot be sufficiently obtained. In the case of using the base material 1 having a small thermal expansion and contraction, the thickness of the photocatalyst layer 3 is set to 35 to 300 nm, preferably 35 to 200 nm, from the viewpoints of ensuring photocatalytic action, preventing cracks, and preventing light interference patterns. I understand that it is important to do.

  The ratio of the total area of the exposed portions 4a of the thermosetting resin to the surface area of the photocatalyst layer 3 is preferably 20 to 99%, and within this range, the exposed portions 4a are finely and almost uniformly scattered. Since the distance between the exposed portions 4a and the area between the exposed portions 4a are appropriately reduced, the friction fastness of the entire surface of the photocatalyst layer 3, particularly the wiping resistance and the scratch resistance are remarkably improved. become. If the ratio of the total area of the exposed part 4a is less than 20%, the area of the photocatalyst layer 3 protected by the exposed part 4a becomes too small, so that it is difficult to improve friction fastness, particularly wiping resistance and scratch resistance. It will be enough. On the other hand, when the ratio of the total area of the exposed part 4a exceeds 99%, the dispersion state of the exposed part 4a is deteriorated, the appearance of the photocatalyst members A1 and A2 is deteriorated, and the ratio occupied by the photocatalyst layer 3 is reduced, resulting in bad odor. There is a risk of degrading the photocatalytic activity such as decomposition of components and low molecular weight organic substances, antibacterial / antifungal activity, and the like. A more preferable ratio of the total area of the exposed portions 4a in the surface of the photocatalyst layer 3 is 20 to 80%, and a more preferable ratio is 25 to 70%.

  The proportion of the exposed portion 4a of the thermosetting resin can be adjusted by the thickness of the protective layer 2 and the crosslinking density of the protective layer 2 as described above, but the protective layer and the photocatalytic layer are formed on the substrate 1 described later. Of the thermosetting resin that adjusts the pressure or the like and moves (exudes) from the substrate 1 to the surface of the photocatalyst layer 3 through the protective layer 2 and the photocatalyst layer 3. By controlling the amount, it can be adjusted within the range of 20-99%. That is, when the amount of the thermosetting resin 4 that migrates (exudes) to the surface of the photocatalyst layer 3 is increased, as shown in FIG. 2, each exposed portion 4a expands to the periphery and the area increases, and the exposed portion 4a. The proportion of occupancy will rise to approach 99%. On the other hand, when the amount of the thermosetting resin transferred (exuded) to the surface of the photocatalyst layer 3 is reduced, as shown in FIG. 1, the individual exposed portions 4a do not expand to the periphery, and the transfer path of the thermosetting resin also becomes Since it becomes thin, the ratio of the exposed portion 4a decreases and approaches 20%.

The contact angle between the surfaces of the photocatalyst members A1 and A2 and water is 30 to 90 ° when measured immediately after irradiating light of 1 mW / cm ² with a black light blue lamp for 168 hours. preferable. From a microscopic viewpoint, strictly speaking, it seems that the exposed portion 4a of the thermosetting resin is different from the surface of the photocatalyst layer 3 between the exposed portions, but the exposed portion 4a is dispersed almost uniformly and finely. Therefore, the contact angle with water on any part of the surface of the photocatalyst member is substantially the same. If the contact angle is 30 to 90 ° as described above, it is one of the photocatalytic actions. Although the self-purifying action due to the hydrophilicity cannot be exhibited, the decomposition action of malodorous components and low molecular weight organic substances, and the antibacterial / antifungal action can be sufficiently exhibited. Further, since the photocatalytic action is not so strong when the contact angle is as described above, the exposed portion 4a of the thermosetting resin is hardly deteriorated or deteriorated by the photocatalytic action even after a long period of time.

  The dispersion form of the exposed portions 4a of the thermosetting resin exposed and scattered on the surface of the photocatalyst layer 3 is not particularly limited. For example, the exposed portions 4a are scattered on the surface of the photocatalyst layer 3 in a state where the exposed portions 4a are individually separated. Or may be dispersed on the surface of the photocatalyst layer 3 in a state where the exposed portions 4a are continuous with each other, or both of these dispersion states may be mixed, but in any of the dispersion forms The exposed portions 4a are preferably dispersed substantially uniformly over the entire surface of the photocatalyst layer 3.

Since the area of the exposed portion 4a of the thermosetting resin varies depending on the dispersion state, it is not particularly limited, but the exposed portion 4a in the state of being separated individually is 1.0 × 10 ^{−4 to} 0.1 mm ^2. When the area is smaller than 1.0 × 10 ⁻⁴ mm ² , the protective action of the photocatalyst layer 3 by the exposed portion 4a may be lowered. On the other hand, when the area is larger than 0.1 mm ^2. In addition, the photocatalytic action, particularly the decomposition of organic matter, is hindered, which may cause inconveniences such as degradation of malodor and antibacterial / antifungal effects.

  Further, the decomposition activity of the malodorous component and the low molecular weight organic substance on the surface of the photocatalyst layer 3 and the strength of the antibacterial / antifungal action are determined by the decomposition activity index R when determined by the methylene blue decomposition test described in the examples below. Is preferably in the range of 3.0 to 5.5 [nmol / l / min]. If the decomposition activity index is within this range, sufficient decomposition action and the like can be exhibited.

  In addition, when the above-mentioned visible light activation particles are included as the photocatalyst particles of the photocatalyst layer 3, the ultraviolet ray absorbent is contained in the thermosetting resin to such an extent that the photocatalytic action is not hindered, and the weather resistance of the exposed portion 4a. You may make it improve property.

  The photocatalyst members A1 and A2 configured as described above are used as building materials and road materials, or as interior members of electrical appliances such as air purifiers, coolers, and refrigerators. When natural light, illumination light, irradiation light, or the like hits the surface of the photocatalyst member, the photocatalyst particles are activated to generate radical species, active oxygen species, and the like, and the photocatalyst layer 3 between the exposed portions 4a of the thermosetting resin is generated. The photocatalytic action is exerted on the surface, and radical species and active oxygen species are scattered on the surface side of the exposed portion 4a to exert the photocatalytic action, so that malodorous components and low molecular weight organic substances are decomposed, antibacterial And defense is done. Moreover, these photocatalyst members A1 and A2 are protected by the exposed portions 4a in which the photocatalyst layer 3 is finely scattered. In particular, most of the exposed portions 4a are connected from the substrate 1 to the surface of the photocatalyst layer 3. Since it is supported by the thermosetting resin 4, it exhibits a great strength against external impact force and friction force, and exhibits excellent protective action, so that the photocatalytic member surface has excellent friction fastness, especially wiping resistance. And the scratch resistance is greatly improved. Accordingly, even if the surface of the photocatalyst member is repeatedly wiped and cleaned, or the object hits the surface of the photocatalyst member, the photocatalyst layer 3 is not peeled off or damaged, and the photocatalytic action is good for a long time. It can be demonstrated.

  FIG. 3 is a schematic cross-sectional view showing still another embodiment of the photocatalyst member according to the present invention.

  This photocatalyst member A3 comprises, as a base material 1, a core layer 1a made of inorganic or organic fibers, a thermosetting resin, and an inorganic filler, and a thermosetting resin-impregnated decorative layer 1b laminated thereon. The photocatalyst layer 3 is laminated on the decorative plate 10 with the protective layer 2 interposed therebetween, and the protective layer and the photocatalyst layer are provided on the thermosetting resin-impregnated decorative layer 1b of the decorative plate 10. Due to the pressure at the time of transfer, the thermosetting resin of the thermosetting resin-impregnated decorative layer 1b passes through the protective layer 2 to the surface of the photocatalyst layer 3 (exudes) and is exposed almost flush with the surface of the photocatalyst layer 3. The exposed portions 4a of the thermosetting resin are scattered almost uniformly on the surface of the photocatalyst layer 1, thereby improving the friction fastness and scratch resistance of the photocatalyst layer 3.

  As the decorative board 10, for example, a glass fiber is impregnated with a thermosetting resin such as a thermosetting melamine resin or a thermosetting phenol resin, and an inorganic filler such as aluminum hydroxide, magnesium hydroxide, calcium carbonate, or talc. Core material layer 1a is formed so as to be 95 to 80% by mass of the whole, and a thermosetting material such as a thermosetting melamine resin on a decorative paper containing titanium oxide is formed on the surface of the core material layer 1a. What laminated | stacked the thermosetting resin impregnation decorative layer 1b impregnated so that it might become 60-150 mass% of resin etc. is used preferably. When the content of the inorganic filler material in the core material layer 1a and the amount of the thermosetting resin impregnated in the thermosetting resin-impregnated decorative layer 1b are within the above ranges, a flame-retardant or non-combustible decorative board 10 is obtained. Can do.

  Since the configuration of the protective layer 2, the photocatalyst layer 3, the exposed portion 4a of the thermosetting resin, and the like of the photocatalyst member A3 are the same as those of the photocatalyst members A1 and A2, the description thereof is omitted.

  The photocatalyst member A3 is such that the decorative board 10 used as the substrate 1 can be made flame retardant or nonflammable, and the exposed portion 4a of the thermosetting resin on the surface of the photocatalyst layer 3 is also a high heat resistant melamine resin. Therefore, it can be a flame-retardant or non-flammable photocatalytic member, and the pattern and design of the thermosetting resin-impregnated decorative layer 1b can be seen through the photocatalyst layer 3 and the protective layer 2, It is suitably used as building materials such as interior materials. And this photocatalyst member A3 also exhibits photocatalytic actions such as decomposition of malodorous components and the like, and antibacterial and antifungal properties by the photocatalyst particles of the photocatalyst layer 3 activated by receiving light, like the photocatalyst members A1 and A2 described above. In addition, since the photocatalyst layer 3 is protected by the exposed portions 4a that are finely dispersed and scattered, the photocatalyst layer 3 is not peeled off or damaged even when repeated wiping or hitting an object. Good photocatalytic action can be maintained.

The photocatalyst members A1, A2, and A3 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. The protective layer 2 and the photocatalyst layer 3 can be laminated on the surface or the entire surface of the substrate 3 having a desired three-dimensional shape other than the shape to form a photocatalyst member having a desired shape.
In addition, none of the above photocatalyst members A1, A2, A3 is provided with an adhesive layer between the base material 1 and the protective layer 2, but in order to increase the bonding strength between the base material 1 and the protective layer 2. An adhesive layer having a thickness that does not hinder the transfer of the thermosetting resin 4 from the substrate 1 to the surface of the photocatalyst layer 3 may be provided. As the adhesive, a resin adhesive that adheres well to both the base material 1 and the protective layer 2 is used.

  Next, the manufacturing method of the present invention will be described by taking as an example the case of manufacturing the photocatalyst member A3.

First, the transfer film which laminated | stacked the photocatalyst layer and the protective layer on the peeling film is produced in the following way.
That is, a coating material for a protective layer (for example, a coating material containing a copolymer resin of the above-mentioned acrylic resin and silicone resin as a main component and a curing agent) and a coating material for a photocatalyst layer (for example, the above-mentioned photocatalyst particles and silica or A coating material prepared by mixing and dispersing a silicone resin and, if necessary, 1% by mass or less of a dispersant in a solvent or water is prepared. And using means such as dip coating, spray coating, spin coating, roll coating, bar coating, etc., the above photocatalyst layer coating material is applied onto a release film such as a polyethylene terephthalate film and dried to a thickness of 5 to 300 nm. Preferably, the photocatalyst layer 3 having a thickness of 5 to 200 μm is formed, and further, the above-mentioned coating material for the protective layer is applied and dried, and the protective layer having a thickness of 0.3 to 5.0 μm, preferably 0.5 to 2 μm. A transfer film is produced by forming a film.

  On the other hand, as a substrate forming material, glass fiber is impregnated with an uncured thermosetting resin such as a thermosetting melamine resin, and an inorganic filler such as aluminum hydroxide or magnesium hydroxide is 95 to 80% by mass of the whole. A material sheet for forming the core material layer 1a of the decorative board 10 (hereinafter referred to as a core material layer forming material sheet) and a decorative paper containing titanium oxide on a thermosetting melamine resin. Material sheet for forming the thermosetting resin-impregnated decorative layer 1b of the decorative board 10 impregnated with an uncured thermosetting resin such as 60 to 150% by mass (hereinafter referred to as a decorative layer forming sheet) Prepare). Then, the decorative layer forming material sheet is overlaid on the core layer forming material sheet, and the transfer film is stacked on the core layer forming material sheet so that the protective layer is on the lower side (the decorative layer forming material sheet side). At the same time, set in a hot press molding machine and thermocompression bond.

  When thermocompression bonding is performed in this manner, the pressure causes the uncured thermosetting resin impregnated in the decorative layer forming material sheet to pass through the protective layer 2 and the photocatalyst layer 3 to the surface of the photocatalyst layer 3 (exudation). Thus, it is exposed on the surface in a finely dispersed state. When the transferred uncured thermosetting resin or the uncured thermosetting resin impregnated in the material sheet is thermoset, the core layer 1a formed by the thermosetting and the thermosetting The resin-impregnated decorative layer 1b is integrated into the decorative plate 10, and at the same time, the protective layer 2 and the photocatalyst layer 3 are transferred and integrated on the surface of the thermosetting resin-impregnated decorative component 1b of the decorative plate 10. Therefore, when this laminated integrated product is taken out from the hot press molding machine and the release film is removed, the beautiful design / pattern of the thermosetting resin-impregnated decorative layer 1b can be seen through the photocatalyst layer 3 and the protective layer 2, and the photocatalyst layer The exposed surface 4a of the thermosetting resin that is transferred and exposed on the surface 3 is scattered, and the flame-resistant or non-flammable makeup excellent in friction fastness (especially wiping resistance) and scratch resistance. The photocatalyst member A3 having properties is obtained.

In the above production method, when the transfer film is produced, the thickness of the protective layer is adjusted as described above, or the crosslink density of the resin forming the protective layer is adjusted, so that the photocatalyst layer 3 is formed at the time of thermocompression bonding. It is preferable to control the amount of the thermosetting resin transferred to the surface of the resin so that it becomes an appropriate amount. It is also preferable to control the amount of the thermosetting resin 4 that moves to the surface of the photocatalytic layer 3 by adjusting the temperature and pressure during thermocompression bonding. The preferred temperature, pressure, time, etc. for thermocompression bonding vary somewhat depending on the type of thermosetting resin, the composition and thickness of the protective layer and the photocatalyst layer, etc., but generally preferred approximate temperature range is 80-160 ° C., pressure The range is 4.9 × 10 ^{6 to} 9.8 × 10 ⁶ N / m ² , and the time is 20 to 100 minutes. The optimum temperature, pressure, and time should be set within these ranges.

The photocatalyst member of the present invention is a method other than the above-described production method of the present invention, for example, the transfer film is set along the inner surface of the mold so that the protective layer is on the inside, and is uncured thermosetting It can also be produced by a method in which a resin is molded in a mold and cured by heating. Also in this case, the uncured thermosetting resin passes through the protective layer by the mold pressure to the surface of the photocatalyst layer, is exposed, and the exposed portion is dispersed on the surface of the photocatalyst layer. Since the curable resin and the transferred thermosetting resin are thermoset, if the release film is removed after demolding, the protective layer 2 is formed on the surface of the thermosetting resin substrate 1 having a three-dimensional solid shape that matches the mold. And a photocatalyst member having good friction fastness and scratch resistance can be obtained.
In addition, a laminate film in which a protective layer and a photocatalyst layer are formed on an adhesive resin film made of acrylic or the like that has been perforated by a process such as punching is produced, and this is laminated on a substrate containing an uncured thermosetting resin. They can also be manufactured by thermocompression bonding. In this case, the uncured thermosetting resin passes through the punching holes, passes through the protective layer 2 and the photocatalyst layer 3 to the surface of the photocatalyst layer, and is exposed, and the exposed portion is scattered on the surface of the photocatalyst layer. Since the thermosetting resin is thermoset in a dispersed state, the adhesive resin film, the protective layer 2 and the photocatalyst member 3 are laminated and integrated on the surface of the thermosetting resin base material 1. A good photocatalytic member can be obtained.

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

[Example 1]
As a substrate forming material, glass fiber is impregnated with an uncured thermosetting melamine resin, and a core material layer forming material sheet containing aluminum hydroxide and calcium carbonate as an inorganic filler, and titanium oxide are contained. A decorative layer forming material sheet in which decorative paper was impregnated with uncured thermosetting melamine resin was prepared.

  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.

  Then, the photocatalyst layer coating material is applied to the surface of the release film made of polyethylene terephthalate, and dried (temperature 100 ° C., time 15 minutes) to form a photocatalyst layer having a thickness of 100 nm. A transfer film was produced by applying a paint and drying (temperature 130 ° C., time 30 minutes) to form a protective layer having a thickness of 3.0 μm.

Next, the decorative layer forming material sheet is overlaid on the core layer forming material sheet, and the transfer film is stacked on the core layer forming material sheet so that the protective layer is on the decorative layer forming material sheet side. Combined with this, it is set in a hot press molding machine, and it is thermocompression bonded for 30 minutes under conditions of a temperature of 140 ° C. and a pressure of 7.8 × 10 ⁶ N / m ² to form an uncured thermosetting melamine resin. The material sheet is transferred to the surface of the photocatalyst layer through the protective layer and the photocatalyst layer (exuded), and is scattered and dispersed to be substantially flush with the transferred thermosetting melamine resin and the above material sheet. The impregnated thermosetting melamine resin was thermally cured to obtain a laminated integrated product in which the core layer, the thermosetting resin impregnated decorative layer, the protective layer, and the photocatalyst layer were integrally joined. Then, this laminated integrated product is taken out from the hot press molding machine, the release film is removed, and the photocatalyst member having the structure shown in FIG. 3, that is, the core material layer 1a composed of thermosetting melamine resin, glass fiber, and inorganic filler. A plate-like photocatalyst member in which a decorative plate 10 in which a thermosetting melamine resin-impregnated decorative layer 1b is laminated and integrated is used as a base material 1, and a protective layer and a photocatalyst layer are transferred thereon and laminated and integrated. Then, the thermosetting melamine resin passed from the decorative layer 1b through the protective layer 2 and the photocatalyst layer 3 to the surface of the photocatalyst layer 3 to obtain a photocatalyst member in which the exposed portions 4a were scattered.

  About the obtained photocatalyst member, when the ratio of the total area of the thermosetting melamine resin exposed part in the surface of the photocatalyst layer was measured by the following test method, the thermosetting melamine resin exposed part was 33% of the surface of the photocatalyst layer. Accounted for.

(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 when the exposed portion of the thermosetting melamine resin is present on the photocatalyst layer, the exposed portion exhibits a light black color due to the silver nitrate reaction in a short time even when the photocatalyst member is irradiated with ultraviolet rays in an aqueous silver nitrate solution. In addition, the place where the thermosetting melamine resin exposed portion does not exist on the photocatalyst layer is based on the property of rapidly exhibiting a light black color due to 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. And the total area of all the thermosetting melamine resin exposure part which occupies the surface of a photocatalyst layer by dividing the total area which developed the above-mentioned light black by the area of the range which calculated the light black colored part The percentage of was calculated.

  FIG. 4 shows a screen after the binarization process in the above test method. As shown in FIG. 4, the light black portions due to the silver nitrate reaction are scattered in spots and react only partially. From this, the thermosetting melamine resin exposed portion is only part of the photocatalyst layer. You can see that it doesn't exist.

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 on the surface of the photocatalyst layer using a microsyringe, and the contact angle of water droplets on the surface is measured by an image processing contact angle meter (Kyowa Interface Science Co., Ltd., CA-A). Each of the three points was measured using a three-point method, and the average value was obtained. As a result, the contact angle was 78 ° before irradiation, but after 24 hours, 48 hours, 72 hours, 120 hours, and 168 hours, 76 °, 74 °, 74 °, and 72 °, respectively. 70 °.

  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 4.9 [nmol / l / min], and the surface of the photocatalyst layer was reached. It was confirmed that the thermosetting melamine resin exerted a good decomposing action even though the thermosetting melamine resin was transferred (welled up) to be exposed and scattered.

(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. 6, 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, for the three test pieces produced by cutting the obtained photocatalyst member, when wiping resistance was examined by the following method, in the initial stage of not wiping, all of the test pieces showed a color reaction of silver nitrate, Even when the number of wipings reached 500 times or even 3000 times, all of the test pieces exhibited a color reaction of silver nitrate. From this, it was found that the photocatalyst layer in which the thermosetting melamine resin exposed portions are scattered is not worn out or detached even after wiping 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.

  The results of the above tests conducted on the photocatalyst member obtained in Example 1 are summarized in Table 1 below. Moreover, the graph of the contact angle with water of this photocatalyst member is shown in FIG. 5, and the change of a methylene blue density | concentration is shown in FIG.

[Example 2]
The photocatalyst layer coating material prepared in Example 1 was applied to the surface of a release film made of polyethylene terephthalate and dried (temperature 100 ° C., time 15 minutes) to form a photocatalyst layer having a thickness of 100 nm. The transfer film was produced by applying the coating for protective layer prepared in 1 and drying (temperature 130 ° C., time 30 minutes) to form a protective layer having a thickness of 1.5 μm.

Then, the decorative layer forming material sheet prepared in Example 1 is overlaid on the core layer forming material sheet prepared in Example 1, and the above-mentioned transfer film is placed on the lower side of the protective film. And then set in a hot press molding machine and thermocompression bonded for 30 minutes under the conditions of a temperature of 140 ° C. and a pressure of 7.8 × 10 ⁶ N / m ² , and then taken out from the hot press molding machine to remove the release film. By removing, a plate-like photocatalyst member having a structure shown in FIG. 3 was obtained.

  About this photocatalyst member, in the same manner as in Example 1, the ratio of the total area of the exposed portion of the thermosetting melamine resin in the surface of the photocatalyst layer, the contact angle with water on the surface of the photocatalyst layer, the decomposition activity of the photocatalyst layer The wiping resistance of the photocatalyst layer was investigated. The results are also shown in Table 1 below.

[Comparative Example 1]
A decorative board (core material layer) obtained by stacking and integrating the core material layer forming material sheet prepared in Example 1 and the decorative layer forming material sheet prepared in Example 1 by thermocompression in advance to cure the melamine resin. And a thermosetting resin-impregnated decorative layer laminated on the base material, and an adhesive (urethane adhesive manufactured by Nippon Polyurethane Industry Co., Ltd.) is coated on the thermosetting resin-impregnated decorative layer of the base material. Agent) is applied and dried to form an adhesive layer having a thickness of 5 μm, and further, the protective layer coating material and the photocatalyst layer coating material prepared in Example 1 are sequentially applied and dried to a thickness of 3 μm. By forming a protective layer and a photocatalyst layer having a thickness of 100 nm, a flat photocatalyst member was produced.

Since this photocatalyst member is formed by applying an adhesive layer, a protective layer and a photocatalyst layer to a decorative board cured by thermocompression bonding, the photocatalyst member is immersed in an aqueous silver nitrate solution and irradiated with ultraviolet rays. There was no thermosetting melamine resin exposed to the surface of the photocatalyst layer, showing a light black color due to a uniform silver nitrate reaction on the entire surface. This is because the thermosetting resin could not be transferred because the adhesive layer, the protective layer, and the photocatalyst layer were formed after the thermosetting resin of the decorative board was cured.

  For this comparative photocatalyst member, the contact angle with water on the surface of the photocatalyst layer, the decomposition activity index of the photocatalyst layer, and the wiping resistance of the photocatalyst layer were examined in the same manner as in Example 1. The results are also shown in Table 1 below. Moreover, the graph of the contact angle of this photocatalyst member with water is also shown in FIG. 5, and the change in the methylene blue concentration is also shown in FIG.

[Comparative Example 2]
The photocatalyst layer coating material prepared in Example 1 was applied to the surface of a release film made of polyethylene terephthalate and dried (temperature 100 ° C., time 15 minutes) to form a photocatalyst layer having a thickness of 100 nm. The transfer film was produced by applying the protective layer coating material prepared in 1 and drying (temperature 130 ° C., time 50 minutes) to form a protective layer having a thickness of 8.0 μm.

  Then, the decorative layer forming material sheet prepared in Example 1 is overlaid on the core layer forming material sheet prepared in Example 1, and the above-mentioned transfer film is placed on the lower side of the protective film. The plate-shaped photocatalyst member was prepared by removing the release film by removing from the heat press molding machine after being superposed and set in a hot press molding machine and thermocompression bonding under the same conditions as in Example 1. . In this photocatalyst member, a protective layer and a photocatalyst layer are transferred and integrated on a decorative board in which a core layer and a thermosetting resin-impregnated decorative layer are laminated and integrated. When immersed in an aqueous solution and irradiated with ultraviolet rays, the entire surface exhibited a light black color due to a uniform silver nitrate reaction, so the thermosetting melamine resin of the decorative layer was not exposed to the surface of the photocatalytic layer through the protective layer, Migration (exudation) of the thermosetting melamine resin was prevented by the protective layer.

  For this comparative photocatalyst member, the contact angle with water on the surface of the photocatalyst layer, the decomposition activity index of the photocatalyst layer, and the wiping resistance of the photocatalyst layer were examined in the same manner as in Example 1. The results are also shown in Table 1 below.

  As shown in Table 1, since the amount of the thermosetting melamine resin that migrates (exudes) to the surface of the photocatalyst layer is slightly small in the photocatalyst member of Example 1 in which the thickness of the protective layer is 3.0 μm, the surface of the photocatalyst layer While the ratio of the total area of the exposed portion of the thermosetting melamine resin in the area is 33%, the photocatalytic member of Example 2 with a slightly thin protective layer thickness of 1.5 μm migrates to the surface of the photocatalytic layer. Since the amount of the thermosetting melamine resin is slightly large, the ratio of the exposed portion of the thermosetting melamine resin is slightly high at 62%. On the other hand, the photocatalyst member of Comparative Example 2 having a thick protective layer of 8 μm has no exposure of the thermosetting melamine resin on the surface of the photocatalytic layer because the migration of the thermosetting melamine resin is blocked by the protective layer. . From the above, when producing a photocatalyst member by thermocompression bonding of a transfer film, the amount of thermosetting melamine resin transferred to the surface of the photocatalyst member is controlled by adjusting the thickness of the protective layer, It can be seen that the ratio of the exposed portion of the curable melamine resin can be controlled. Moreover, in order to control the ratio for which the thermosetting melamine resin exposure part accounts for 20 to 99%, it can be predicted that the thickness of the protective layer may be about 0.3 to 5.0 μm.

  Moreover, the thermosetting melamine resin is exposed and scattered on the surface of the photocatalyst layer, and the photocatalyst member of Examples 1 and 2 in which the ratio of the exposed portion is within a range of 20 to 99% is irradiated with ultraviolet rays for 168 hours. The contact angle with water after the treatment is 70 ° or more, and the self-purifying action due to the hydrophilicity cannot be exhibited, but the decomposition activity index R is 4.9 [nmol / nm for the photocatalyst member of Example 1. l / min], which is 3.5 [nmol / l / min] in the photocatalyst member of Example 2, and it can be seen that sufficient decomposing action of malodorous components and low molecular weight organic substances can be exhibited. In addition, the photocatalyst member of Examples 1 and 2 in which the thermosetting melamine resin is exposed and scattered on the surface of the photocatalyst layer sufficiently withstands 3,000 wiping resistance tests and prevents the photocatalyst layer from falling off and peeling off, and is a good photocatalyst It can be seen that the action can be maintained.

  In contrast, the photocatalyst layers of Comparative Examples 1 and 2 in which no thermosetting melamine resin is present on the surface of the photocatalyst layer are strongly hydrophilic because the contact angle with water after irradiation with ultraviolet rays for 48 hours is close to 0 °. And can exhibit a self-cleaning action, and the decomposition activity index is as high as 6.5 [nmol / l / min] or 6.2 [nmol / l / min], so that the photocatalytic action can be exerted strongly. However, since it is inferior in wiping resistance, it cannot withstand only 500 wiping resistance tests, and has a fatal defect that the photocatalytic layer is peeled off and dropped off in a short period of time and the photocatalytic action is lost. I understand.

It is a schematic cross section which shows one Embodiment of the photocatalyst member which concerns on this invention. It is a schematic cross section which shows other embodiment of the photocatalyst member which concerns on this invention. It is a schematic cross section which shows other 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) with water and ultraviolet irradiation time (hour) about the sample of Example 1 and the sample of Comparative Example 1. The data obtained in the methylene blue decomposition test for the sample of Example 1 and the sample of Comparative Example 1 are plotted, and the methylene blue test solution concentration C (t) [μmol / l], the ultraviolet irradiation time (min), and It is the graph which showed this relationship.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Base material 1a Core material layer 1b Thermosetting resin impregnation decorative layer 2 Protective layer 3 Photocatalyst layer 4 Connection thermosetting resin 4a Exposed part of connection thermosetting resin A1, A2, A3 Photocatalyst member

Claims (8)

  A photocatalyst layer containing photocatalyst particles is laminated via a protective layer on a base material made of a thermosetting resin or a base material containing a thermosetting resin, and the thermosetting resin is formed on the surface of the photocatalyst layer. A photocatalyst member scattered in an exposed state, wherein at least a part of the exposed thermosetting resin continues to the substrate through the photocatalyst layer and the protective layer.     A photocatalyst layer containing photocatalyst particles is laminated via a protective layer on a base material made of a thermosetting resin or a base material containing a thermosetting resin, and the thermosetting resin is formed on the surface of the photocatalyst layer. A photocatalyst member scattered in an exposed state, wherein at least a part of the exposed thermosetting resin is transferred from the substrate through the protective layer and the photocatalyst layer to the surface of the photocatalyst layer. Photocatalyst member.   The photocatalyst member according to claim 1 or 2, wherein the protective layer has a thickness of 0.3 to 5.0 µm.   The photocatalyst member according to any one of claims 1 to 3, wherein the ratio of the total area of the exposed portions of the thermosetting resin 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 a contact angle with water on the surface after irradiating light of 1 mW / cm ² with black light blue for 168 hours is 30 to 90 °. .   6. The decorative board according to claim 1, wherein the base material is a decorative board in which a thermosetting resin-impregnated decorative layer is laminated and integrated on a core layer made of fibers, a thermosetting resin, and an inorganic filler. Photocatalytic member.   The photocatalyst member according to any one of claims 1 to 6, wherein the thermosetting resin is a thermosetting melamine resin.   A transfer film is prepared by sequentially forming a photocatalyst layer containing a photocatalyst particle and a protective layer on a release film, and the transfer film is formed on a substrate forming material containing an uncured thermosetting resin. By overlapping and thermocompression bonding so as to be on the base material side, the uncured thermosetting resin is transferred from the base material forming material to the surface of the photocatalyst layer through the protective layer and the photocatalyst layer. A method for producing a photocatalyst member, wherein the protective layer and the photocatalyst layer are transferred onto a base material formed by being exposed and scattered on a surface and thermosetting an uncured thermosetting resin.

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