KR102130431B1 - Sport field flooring comprising visible light active photocatalys - Google Patents

Abstract

The present invention relates to sports flooring containing visible light active photocatalysts. According to one aspect of the present invention, the sports flooring containing the visible light active photocatalysts includes: a base frame in a flat plate shape; and an impact absorbing part mounted on one surface of the base frame, wherein the base frame is formed by allowing the photocatalysts to be dispersed. The photocatalysts include: inorganic oxides; and organic metal compound derived metal oxide layers formed on the inorganic oxides. The photocatalysts have photoactivity in a visible light area of 400 nm or more.

Description

Sports flooring material containing visible light active photocatalyst {SPORT FIELD FLOORING COMPRISING VISIBLE LIGHT ACTIVE PHOTOCATALYS}

The present invention relates to a sports flooring material comprising a photocatalyst having an expanded catalytically active wavelength range. More specifically, the present invention relates to a prefabricated playground flooring, and relates to a flooring installed on an indoor or outdoor floor.

Prefabricated playground flooring by plastic injection started developing and mass-producing in the United States for the first time in the late 1970s and has been used as a replacement for the existing hard court.

These prefabricated playground floorings are available in a variety of colors and in various designs, and with the appearance of high-performance sunscreens and antioxidants, they can not only provide excellent weather resistance to plastic products, but also design the surface as a drainable structure, even though it is an outdoor coat. The water is not condensed and all-weather coat is made. Through various designs of the surface shape, it is possible to select and use the sliding characteristics according to the movement characteristics.

Therefore, the flooring material of the playground has been improved and has been widely applied not only for use as a playground flooring material, but also for walking trails, roofs of buildings, verandas, toilets, parking lots, garages, warehouses, and bicycle roads.

Existing products are injection molded in one color with a single type of resin, so they try to absorb shock by structural design of the injection molded product, but they are far below DIN18032 Part II, which is a shock absorbing standard for playground or court flooring.

In addition, it is inevitable to design a coat using prefabricated characteristics, and since it uses 100% polypropylene (PP) resin as a raw material, a hard feeling cannot be avoided. To this end, the existing prefabricated playground flooring material has a hash characteristic of the PP resin itself, so that it can properly mix polyethylene (PE) to give a sliding characteristic, but it has a dot pattern on the surface considering the characteristics of each sports type. In some cases, the sliding characteristics are controlled by regularly placing or embossing diagonal lines on a linear surface structure or by adjusting the angle of the lines.

In addition, these injection products used as flooring materials of existing sports grounds are very poor in terms of the ability to absorb shock, which is one of the required characteristics as a flooring material. This is equivalent to 6-20%, far below the 53% stipulated in the relevant standard, DIN 18032 Part II.

In addition, the existing prefabricated playground flooring has no problem in drainage because all the products have a reticular structure, but it is not easy to remove when infiltrating foreign substances, and there is anxiety such as stuck Stud or high heels on the heels when walking or exercising. There is also a phenomenon that may cause injury if the skin of the skin is pushed into the concave area when it falls during an athletic event and the skin is pushed in. Depending on the angle of the dots or diagonal lines introduced into the surface for the purpose of preventing slippage and the angled corners of the linear corners, it can also cause abrasions during falling during sports or walking.

As the demand for improvement on the sports flooring increased, the sports flooring began to be applied even outdoors, and in the outdoor sports scene with the sports flooring, lights were installed to improve the disadvantages of difficulty in exercising at night (outdoor basketball court) Etc). However, the light consumed a lot of power, and excessively dazzling in the process of exercising, or reached complaints from residents around the city due to light pollution.

In addition, air pollution has become a major problem in recent years when sports lovers exercise. A photocatalyst is a technique for eliminating such air pollution. The photocatalyst has catalytic activity by absorbing light energy and oxidatively decomposes environmental pollutants such as organic substances with strong oxidizing power by catalytic activity. That is, the photocatalyst, by irradiating light (ultraviolet rays) having energy of a band gap or more, a transition of electrons from a valence band to a conduction band occurs, and a hole is formed in the valence band. These electrons and holes diffuse to the surface of the powder, and react with oxygen and moisture to cause a redox reaction or recombine to generate heat. That is, electrons in the conduction band reduce oxygen to generate superoxidion ions, and holes in the valence band oxidize moisture to form hydroxy radicals (OH·). With the strong oxidizing power of hydroxy radicals (OH·) generated by these holes, it is possible to exhibit decomposition, sterilizing power, hydrophilicity, etc. of gaseous or liquid organic substances adsorbed on the surface of the photocatalyst, that is, difficultly decomposing organic substances. In general, titanium dioxide (TiO ₂ ) powder is used as a photocatalyst, and titanium dioxide (TiO ₂ ) has the advantages of being harmless to the human body, having excellent photocatalytic activity, excellent light corrosion resistance, and low price. Titanium dioxide (TiO ₂ ) absorbs and reacts with ultraviolet rays of 388 nm or less to generate electrons (conduction bands) and holes (valence bands). In this case, ultraviolet rays used as light sources include lamps, incandescent lamps, mercury lamps Artificial lighting, light emitting diodes, and the like can be used. The electrons and holes generated in the reaction recombine in 10 ^-12 to 10 ^-9 seconds, but if contaminants or the like adsorb on the surface before recombination, they are decomposed by the electrons and holes. However, the band gap energy (wavelength of 380nm or more) of titanium dioxide (TiO ₂ ) powder is obtained from sunlight, and since about 2% of the light can be used, smooth catalytic activity in the visible wavelength (400~800nm), which is the main wavelength of sunlight Have difficulty having That is, in order to respond to visible light, it is essential to effectively reduce the band gap of the photocatalyst and to efficiently separate the electron/hole pairs generated through light absorption, but the efficiency is still in the visible light-sensitive photocatalyst of titanium dioxide (TiO ₂ ) powder. It is not reaching the level to be commercialized in the air cleaning field.

On the other hand, as the modern society becomes more serious, air pollution is getting serious, and people's demand for improving air quality is continuously increasing. In addition, the risk of disease increases due to the recent emergence of highly infectious viruses, and the need for antibacterial and antiseptic products that are harmless to the human body is due to the toxicity issues of humidifier disinfectants.

In this aspect, the application of air purification technology using a photocatalyst to various applications has received much attention. However, in the case of a general-purpose product in the form of a powder or a coating liquid, there is a problem in that the performance difference is large depending on the site to be applied, and a product such as an air purifier equipped with a photocatalyst and a light source has a disadvantage that various applications are impossible.

Therefore, there has been a demand for users for products applied with a photocatalyst that exhibits high activity even under the light of visible light in combination with an illumination or light emitting device that emits light in the visible light region.

The present invention is to solve the above-described problems, the present invention is developed by introducing a doping process of an organometallic compound, having an excellent photocatalytic activity in the visible light region, to develop an inorganic oxide-based photocatalyst, and applied it as a sports flooring It is done.

An embodiment of the present invention is to apply the photocatalyst comprising an inorganic oxide-based photocatalyst to the present invention to a sports flooring material including a lighting device or display for emitting light.

One embodiment of the present invention is to provide a sports flooring material comprising an inorganic oxide-based photocatalyst, and having a photolysis function to provide air purification performance.

According to an embodiment of the present invention, an inorganic oxide-based photocatalyst is manufactured using a doping process of an organometallic compound, and the thus prepared photocatalyst is applied to a sports flooring material to automatically purify the air in the surrounding space for exercise. It is to form a sports space.

However, the problems to be solved by the present invention are not limited to those mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

Sports flooring material comprising a visible light active photocatalyst according to an aspect of the present invention, a flat base frame; And a shock absorber mounted on one surface of the base frame, wherein the base frame is formed by dispersing a photocatalyst, and the photocatalyst comprises an inorganic oxide and a metal oxide layer derived from an organometallic compound formed on the inorganic oxide. It has photoactivity in the visible light region of 400 nm or more.

According to an embodiment of the present invention, the flat base frame may be formed by dispersing the photocatalyst in a weight range of 1 to 99% by weight in a polypropylene-based resin matrix.

According to an embodiment of the present invention, the flat base frame may include a plurality of drain holes formed by patterning.

According to an embodiment of the present invention, the shock absorber may include one or more selected from the group consisting of polypropylene, polypropethylene, metallocene and thermoplastic elastomer (TPE).

According to an embodiment of the present invention, further comprising a light-emitting portion provided on the lower portion of the flat base frame, the light-emitting portion may include an optical fiber, LED or both.

According to an embodiment, a coating layer (not shown) including the photocatalyst may be formed on at least a portion of the flat base frame.

According to an embodiment, the metal oxide layer may include ferrocene-derived iron oxide.

According to one embodiment, the inorganic oxide is to include at least one selected from the group consisting of oxides containing at least one of Ti, Zn, Al and Sn, the metal oxide layer is 0.001 to 10 weight compared to the inorganic oxide % Iron oxide, and the photocatalyst may have photoactivity under dry conditions of 30% or less humidity.

According to an embodiment, the inorganic oxide may include at least one selected from the group consisting of beads, powder, rod, wire, needle, and fiber, and the size of the inorganic oxide may be 1 nm to 500 μm.

According to one embodiment, the inorganic oxide does not include an inorganic oxide containing iron, and the iron oxide layer may be a ferrocene deposited on the inorganic oxide being heat-treated.

According to one embodiment, the metal oxide may include one or more of the compounds represented by Formula 1 below.

[Formula 1]

Me _x O _Y H _Z

(Me is one or more metal elements of groups 1 to 3, X, Y and Z are each selected from 0 to 3, and X and Y are not 0.)

According to an embodiment, the specific surface area of the photocatalyst may be 5 (m ² /g) or more, and the average pore size may be 50 nm or less.

According to the present invention, an inorganic oxide-based photocatalyst having excellent photocatalytic activity in the visible light region and excellent photodecomposition efficiency in various humidity and temperature regions can be prepared, and by using this, a sports flooring material having an air purification function can be manufactured. .

The sports flooring material including the visible light-activated photocatalyst proposed in the present invention may be activated by receiving light including a visible light region.

The present invention can provide a sports flooring material including an inorganic oxide-based photocatalyst in a simple and economical manner, and the sports flooring material provided with the inorganic oxide-based photocatalyst includes a photocatalyst that can be activated even under dry conditions. It has the ability to decompose volatile organic compounds with high efficiency in response to light in the visible light region, and has excellent shock-absorbing properties and durability.

In addition, according to an embodiment, the sports flooring includes a lighting device such as an optical fiber and an LED to form a structure that emits light when electricity is turned on, thereby enabling outdoor exercise even in a night environment without lighting, or at night. You can expect the effect of checking the line during a sports event.

1A and 1B are conceptual views showing one possible form of the structure of a sports flooring material including a visible light active photocatalyst according to an embodiment of the present invention, a perspective view from above (FIG. 1A) and a perspective view from below ( 1b).
Figure 2 shows a flow chart of a method for producing a photocatalyst according to the present invention, according to an embodiment of the present invention.
FIG. 3 exemplarily shows a configuration of a TR-CVD reactor used in the manufacturing process of a photocatalyst according to the present invention, according to an embodiment of the present invention.
Figure 4, according to an embodiment of the present invention, illustratively shows the manufacturing process of the photocatalyst used in the present invention.
5 shows an image of a photocatalyst prepared according to an embodiment of the present invention.
6 shows a TEM image of a photocatalyst prepared according to an embodiment of the present invention.
Figure 7 shows the evaluation results of the photolysis performance of the photocatalyst prepared according to the embodiment of the present invention.
Figure 8 shows the evaluation results of the photolysis performance according to the humidity of the photocatalyst prepared according to the embodiment of the present invention.
Figure 9 shows the results of the stability evaluation of the photolysis performance according to the repeated photolysis experiments of the photocatalyst prepared according to the embodiment of the present invention.

Hereinafter, embodiments will be described in detail with reference to the accompanying drawings.

Various modifications may be made to the embodiments described below. The examples described below are not intended to be limiting with respect to the embodiments, and should be understood to include all modifications, equivalents, or substitutes thereof.

The terms used in the examples are only used to describe specific examples, and are not intended to limit the examples. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this specification, terms such as “include” or “have” are intended to indicate that there are features, numbers, steps, operations, components, parts, or combinations thereof described in the specification, and one or more other features. It should be understood that the existence or addition possibilities of fields or numbers, steps, operations, components, parts or combinations thereof are not excluded in advance.

Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by a person skilled in the art to which the embodiment belongs. Terms, such as those defined in a commonly used dictionary, should be interpreted as having meanings consistent with meanings in the context of related technologies, and should not be interpreted as ideal or excessively formal meanings unless explicitly defined in the present application. Does not.

In addition, in the description with reference to the accompanying drawings, the same components are given the same reference numerals regardless of the reference numerals, and redundant descriptions thereof will be omitted. In describing the embodiments, when it is determined that detailed descriptions of related known technologies may unnecessarily obscure the subject matter of the embodiments, the detailed descriptions will be omitted.

In addition, terms used in the present specification are terms used to appropriately represent a preferred embodiment of the present invention, which may vary depending on a user, an operator's intention, or a custom in the field to which the present invention pertains. Therefore, definitions of these terms should be made based on the contents throughout the present specification. The same reference numerals in each drawing denote the same members.

Throughout the specification, when one member is positioned “on” another member, this includes not only the case where one member abuts another member, but also the case where another member exists between the two members.

Throughout the specification, when a part “includes” a certain component, it means that the other component may be further included instead of excluding the other component.

Hereinafter, the inorganic oxide-based photocatalyst of the present invention will be described in detail with reference to examples and drawings. However, the present invention is not limited to these examples and drawings.

1A and 1B are conceptual views showing one possible form of the structure of a sports flooring material including a visible light-activated photocatalyst according to an embodiment of the present invention, a perspective view from above (FIG. 1A) and a perspective view from below ( 1b).

Hereinafter, with reference to Figures 1a and 1b shown as one form of the present invention, each configuration constituting the present invention will be described in detail. However, the shape of the sports flooring illustrated in FIGS. 1A and 1B is merely an example, and the sports flooring proposed in the present invention is not limited to the shapes illustrated in FIGS. 1A and 1B.

Sports flooring 10 comprising a visible light active photocatalyst according to an aspect of the present invention, the flat base frame 10; And a shock absorber 30 mounted on one surface of the base frame, wherein the base frame is formed by dispersing a photocatalyst, and the photocatalyst is an inorganic oxide and a metal oxide layer derived from an organic metal compound formed on the inorganic oxide It includes and has a photoactive in the visible region of 400 nm or more.

As an example, the base frame may include a projection 20. The protrusion may have a length of 1 mm to 5 mm. The protrusion may be provided to contact the indoor or outdoor floor. The shock transmitted from the base frame to the protrusion may be absorbed by the protrusion being pressed or bent.

The base frame and the protrusion may be formed using an injection or blow molding method using the same resin.

As an example, the shock absorber may be hardened as it is cooled by being combined and cooled using a double injection method on one surface of the base frame when the base frame is injected. At this time, the double injection method may be to form an elastic body having a plate-like structure on the base frame using an overmolding method or the like.

The base frame 10 may be formed in a flat frame shape. The base frame 10 is installed indoors or outdoors, and can be used as a platform for people. When people use the base frame as a scaffold, the base frame can absorb the shock by self-bending the force exerted by the foot.

The base frame may include a plurality of seating grooves, and the shock absorbing portion may be seated in the seating groove.

According to an embodiment of the present invention, the flat base frame may be formed by dispersing the photocatalyst in a weight range of 1 to 99% by weight in a polypropylene-based resin matrix.

As an example, the base frame may be formed of a polypropylene resin material having an ethylene content of 18% to 25%.

It is preferable that the base frame simultaneously contains toughness and flexibility even at low temperatures, thereby improving weight bearing capacity and shock absorption capacity. At this time, when the ethylene content of the base frame is less than 18%, the ability to support the weight may be improved, but due to lack of flexibility, the shock absorption can be reduced to less than the standard, and formed larger than 25% of the ethylene content of the base frame If possible, the shock absorption can be increased, but the durability can be significantly reduced due to the weak weight bearing capacity.

The base frame may further include polypropylene (PP) or polyethylene (PE), which is an olefin-based resin. As an example, the base frame may be manufactured by containing Talc so that shrinkage and expansion are small, as is well known.

It is preferable that the shock absorber is formed with a hardness lower than that of the base frame. The base frame is formed of a rigid polypropylene resin material so as to have a hash (Hash) characteristic, to support the weight applied from the human foot, the shock absorbing portion is formed lower than the hardness of the base frame is the human foot It can be induced to better absorb the shock applied from the.

According to an embodiment of the present invention, the flat base frame may include a plurality of drain holes formed by patterning.

The base frame may include a plurality of drain holes 11. The drain hole may have a plurality of slits spaced apart from each other. At this time, water or foreign matter may be discharged through the drain hole to the bottom of the base frame.

According to an embodiment of the present invention, the shock absorber may include one or more selected from the group consisting of polypropylene, polypropethylene, metallocene and thermoplastic elastomer (TPE).

The impact absorbing portion may be manufactured using resins such as EVA, PE-LD, TPR, PP Metallocene, PE-Metallocene, TPE-V, TPE-S, in consideration of adhesion to the base frame. In addition, it may be preferable that the Shore A hardness is a resin capable of producing elasticity of about 50 to 70 degrees.

The shock absorbing portion may be formed of a resin material having a Shore A hardness of 50 to 70. When the base frame is bent by an impact in a state where the shock absorber is combined with the base frame, it may be designed to increase the shock absorbing amount to the maximum by bending together with the base frame.

When the shock absorber is formed with a Shore A hardness of less than 50, it becomes a soft material, so it is not shock absorbing in connection with the bending of the base frame, but rather shock absorbing due to its own off. Absorption amount drops significantly. On the other hand, if the shock absorber is formed to be greater than Shore A hardness 70, the shock absorber becomes too hard (Hash) and interlocks with the curvature of the base frame.The shock absorber is separated from the base frame due to the distortion of the base frame or the base frame. When it is composed of bays, it may not be possible to exert a shock absorption amount similar to the shock absorption amount.

According to an embodiment of the present invention, further comprising a light-emitting portion provided on the lower portion of the flat base frame, the light-emitting portion may include an optical fiber, LED or both.

According to an embodiment, the light emitting unit may form a connection with a power source, and receive the electricity, so that the sports flooring unit emits light. In addition, when the light-emitting portion emits light, it can receive light and activate the photocatalyst while simultaneously illuminating the surroundings. At this time, the light emission of the sports flooring unit may be simply light emission for inducing the activity of the photocatalyst, or on the other hand, light emission as a display or light emitting device for helping sports or aesthetics by emitting light to the outside.

The light emitting unit may be formed to be dispersed in a dot pattern or a line pattern under the flat base frame.

According to an embodiment, a coating layer including the photocatalyst may be formed on at least a portion of the flat base frame. The photocatalyst coating layer formed on some surfaces of the flat base frame may have a thickness of 1 mm to 5 mm.

The photocatalyst portion may include an inorganic oxide and a metal oxide layer formed thereon. In this case, the inorganic oxide and the metal oxide layer are referred to as a photocatalyst. The photocatalyst may or may not be in the form of particles. Unlike the conventional photocatalysts, the photocatalyst is characterized by having an active photoactivity by reacting with a wavelength of a visible light region of 400 nm or more. This may be an effect implemented in a metal oxide layer derived from an organometallic compound.

According to an embodiment, the metal oxide layer may include ferrocene-derived iron oxide. The organometallic compound may be ferrocene as an example, and the metal oxide layer may include iron oxide derived from ferrocene.

According to an embodiment, the photocatalyst portion may be to form a coating layer on the surface of the sports flooring portion. The photocatalyst part may be provided by directly forming a coating layer on the light emitting surface of the sports flooring part.

According to one embodiment, the photocatalyst unit, as the photocatalyst is coated on a base substrate, includes a structure of at least one of a film, a block and a protrusion type or a structure in a particle form formed by coating the photocatalyst on a base particle, The photocatalyst portion may be formed spaced apart from the surface of the sports flooring portion. According to another exemplary embodiment, the photocatalyst part may be provided in various forms spaced apart from the surface of the sports flooring part. In the present invention, the photocatalyst part is not related to anything as long as it is a position and a shape to which light emitted from the sports flooring part can be transmitted, and the present invention is not particularly limited in this regard.

The base substrate does not specifically limit the material in the present invention. As an example, it may be an inorganic material containing silicon, a plastic-based organic material, or an organic-inorganic composite material.

As an example, the photocatalyst unit may receive light energy from an auxiliary light source by using an additional lighting component as well as a sports flooring unit.

According to one embodiment, the power supply unit, the sports flooring unit and the photocatalyst unit are provided in a housing, and further include one or more inlets for introducing air to the photocatalyst unit in the housing, or one surface of the photocatalyst unit is exposed toward the outside of the housing It may have been done.

According to one embodiment, the inorganic oxide is to include at least one selected from the group consisting of oxides containing at least one of Ti, Zn, Al and Sn, the metal oxide layer is 0.001 to 10 weight compared to the inorganic oxide % Iron oxide, and the photocatalyst may have photoactivity under dry conditions of 30% or less humidity.

The photocatalyst, inorganic oxide; And a metal oxide layer formed on the inorganic oxide. Including, and the inorganic oxide may include at least one selected from the group consisting of oxides containing at least one of Ti, Zn, Al and Sn.

The metal oxide layer may include a ferrocene-derived iron oxide layer. At this time, the content of iron may be preferably 0.001 to 5% by weight relative to the inorganic oxide.

The inorganic oxide is an inorganic semiconductor compound that absorbs light energy and exhibits catalytic activity. For example, Ti, Zn, Al, Fe, W, Sn, Bi, Ta, Cu, Si, Ru, Sr, Ba, and Ce It is an oxide containing at least one selected from the group consisting of, it may be preferably Ti, Zn, Al and Sn. Specifically, TiO ₂ , Al ₂ O ₃ , ZnO ₂ , ZnO, SrTiO ₃ , Fe ₂ O ₃ , Ta ₂ O ₅ , WO ₃ , SnO ₂ , Bi ₂ O ₃ , NiO, Cu ₂ O, SiO, SiO ₂ , MoS ₂ , InPb, RuO ₂ , CeO _{2 and the} like. In addition, semiconductor compounds such as CdS, GaP, InP, GaAs, and InPb may be further included in addition to the oxide.

The inorganic oxide may include at least one selected from the group consisting of beads, powder, rod, wire, needle, and fiber, and the size of the inorganic oxide is 1 nm or more; 10 nm or more; 30 nm to 500 μm; 30 nm to 100 μm; Or 30 nm to 1 μm. The size may mean diameter, thickness, length, etc., depending on the shape.

As an example, the metal oxide layer derived from the metal organic compound may be formed by a ferrocene doping process. For example, the ferrocene layer formed on the inorganic oxide may be thermally decomposed to ferrocene, and may include iron oxide converted from ferrocene by the thermal decomposition process. The doping process of the organometallic compound will be described in more detail in the following manufacturing method.

The metal oxide layer derived from the organic metal oxide may be, for example, iron oxide derived from at least one of ferrocene and ferrocene derivatives. The ferrocene derivatives include ferrocene aldehyde, ferrocene ketone, ferrocene carboxylic acid, ferrocene alcohol, phenol or ether compound, nitrogen-containing ferrocene compound, sulfur-containing ferrocene compound, phosphorus-containing ferrocene compound, silicon-containing ferrocene compound, 1,1' -In the group consisting of 1,1'-di-copper ferrocene, ferrocene boric acid, ferrocenyl cuprous acetylide and bisferrocenyl titanocene It may include at least one selected.

As an example, the metal content in the metal oxide layer derived from the organometallic compound is 0.001 to 10% by weight compared to the inorganic oxide; 0.01 to 10% by weight; 0.01 to 3% by weight; 0.01 to 1.5% by weight; Or 0.01 to 1% by weight. When included in the above range, photocatalytic activity in the visible light region may be increased to improve photolysis efficiency. In addition, although the absorption of the visible region may increase when the content of the metal increases, it is preferable to include the content of the metal within the above range, and more preferably, since the decrease in the photocatalytic activity may occur due to the increase in the content of the metal. The metal is iron, and the content of the iron may be 0.01 to 5% by weight.

As an example, the metal oxide layer derived from the organometallic compound may be 0.01 nm or more; 0.1 nm or more; 10 nm or more; Or it may have a thickness of 1 nm to 100 nm. When included in the above thickness range, the porosity of the photocatalyst can be prevented due to the increase in the thickness of the coating layer, and the amount of adsorption of moisture, OH- ions, and decomposition targets on the surface can be increased to improve the photodegradation performance. In addition, the metal oxide layer derived from the organometallic compound, 0.01 nm or more; 0.1 nm or more; 10 nm or more; Or it may include ferrocene-derived iron oxide having a size of 1 nm to 100 nm. The size may mean length, diameter, thickness, and the like depending on the shape.

According to one embodiment, the inorganic oxide does not include an inorganic oxide containing iron, and the iron oxide layer may be a ferrocene deposited on the inorganic oxide being heat-treated.

The metal oxide derived from the organometallic compound may include one or more of the compounds represented by Formula 1 below.

[Formula 1]

Me _x O _Y H _Z

Here, Me is at least one of the metal elements corresponding to groups 1 to 3, X, Y and Z are each selected from 0 to 3, and X and Y are not 0. As an example, a photocatalyst that responds to visible light by absorbing light in the visible light region and introducing a stable and inexpensive semiconductor material, iron oxide (Fe _x O _y H _z ), in the form of nano-sized particles into the TiO ₂ surface Can form.

According to an embodiment of the present invention, in the photocatalyst, a wavelength region exhibiting a photoreaction by absorbing light may be extended from ultraviolet light to visible light. The photocatalyst can exhibit much better photocatalytic activity than conventional photocatalysts, especially in the visible light region of 400 nm or more. In addition, the photocatalytic reactivity capable of adsorption and decomposition of the decomposition target on the surface is improved to have a photocatalytic activity in various humidity regions, and may exhibit excellent photocatalytic activity even in dry conditions of 30% or less humidity.

According to an embodiment of the present invention, the photocatalyst, 5 (m ² /g) or more; 5 (m ² /g) to 1000 (m ² /g); Or it has a specific surface area of 5 (m ² /g) to 100 (m ² /g), and the average pore size may be 50 nm or less. According to one embodiment, by introducing a metal oxide derived from an organometallic compound on the surface of the inorganic oxide, the amount of adsorption target to be decomposed on the surface of the photocatalyst is increased, and the photocatalytic reactivity is increased to improve the efficiency of the photocatalyst.

According to one embodiment of the present invention, the photocatalyst is applied to the decomposition of various harmful substances, that is, it can be used for treatment of environmental pollutants, odor substances, organic compounds, acid gases, and the like. For example, it is used for adsorption and/or photolysis of at least one of gas, liquid, and solid materials, and may exhibit photoactivity by light energy including various light rays such as halogen lamps, xenon lamps, sunlight, and light emitting diodes. More specifically, as the gas, VOCs (volatile organic compounds) such as acidic, basic gas, acetaldehyde, ketones, hydrocarbons of aromatic hydrocarbons and aliphatic hydrocarbons (Paraffin-based and Olefin-based), ozone gas, organic And inorganic glass gas, and more specifically, carbon dioxide, carbon monoxide, NOx, SOx, HCl, HF, NH ₃ , methylamine, formaldehyde, hydrogen sulfide, amine, methylmergaptan, hydrogen, oxygen, nitrogen, methane, paraffin , Olefin, and the like. Examples of the liquid include formaldehyde, acetaldehyde, benzene, toluene, methyl ethyl ethyl ketone (MEK), trichloroethylene, disinfectant, gasoline, diesel, oil, alcohol, Phenol, dye, and the like, and the solid may be a transition metal, a precious metal such as Pt, Pd, ions and/or particles such as Hg, Cr, nanoparticles of 100 nm or less, but is not limited thereto.

The photocatalyst is provided with the photocatalyst composition, and may be included in 0.01 to 99% by weight of the photocatalyst composition. The photocatalyst composition may be formed as a coating layer in one embodiment to form a part of the photocatalyst part.

As an example, the photocatalyst composition may include an aqueous solvent, an oily solvent, or both in a residual amount, and may be appropriately selected according to application fields. For example, it may be a lower alcohol of C ₁ -C ₄ such as water, tanol, ethanol, propanol, isopropanol, butanol, but is not limited thereto.

The photocatalyst composition, if it does not deviate from the object of the present invention, may further include additives according to performance improvement and application fields, and may further include a surfactant, a siloxane-based binder, an antibacterial agent, a disinfectant, etc. It is not mentioned.

The photocatalyst composition may be coated on a substrate or molded into various shapes. For example, the substrate may include cellulose paper; Synthetic wood, wood; fiber; textile; And metal, polymer resin or glass, powder of glass, sheet, film or beads; It may include one or more selected from the group consisting of, but is not limited thereto.

According to an embodiment of the present invention, the present invention relates to a sports flooring product or device having a photocatalytic function by including the photocatalyst described above. The sports flooring product or device, in addition to the basic function of luminescence, may also exhibit an air purifying function together with a photocatalytic function. For example, it may be one having a photodegradation function and/or an air purification function by photoactivity such as volatile substances, odor substances, and contaminants.

According to an embodiment of the present invention, the photocatalyst unit may be a molded body comprising the photocatalyst or the photocatalyst bound on a substrate.

For example, the photocatalyst portion may be a substrate coated with a photocatalyst or photocatalyst composition, an impregnated substrate, a molded substrate, a solid comprising a photocatalyst or photocatalyst composition, a liquid, or a formulation comprising the two.

For example, the formulation may be a powder, solid, suspension, emulsion, cream, ointment, gel, liquid formulation, etc., but may be, for example, ink, paint, or dye, but is not limited thereto.

Figure 2, according to an embodiment of the present invention, shows a flow diagram of a method of manufacturing an inorganic oxide-based photocatalyst according to the present invention.

Hereinafter, with reference to FIG. 2, a description will be given of a method of manufacturing a photocatalyst included in the sports flooring.

According to an embodiment of the present invention, the method for preparing the photocatalyst comprises: preparing an inorganic oxide; Forming a metal oxide layer on the inorganic oxide; And forming a metal oxide layer derived from an organic metal oxide by heat treatment after the step of forming the metal oxide layer.

The preparing of the inorganic oxide is a step of preparing an inorganic oxide dispersion or coating an inorganic oxide on a substrate, wherein the dispersion is an aqueous solvent, an oily solvent, or a mixture of the two, and the substrate is a silicon substrate , A wafer, a glass substrate, a semiconductor substrate, a metal substrate, and the like. The inorganic oxide may be applied by spin coating, roll coating, spray coating, dip coating, flow coating, doctor blade method, or the like.

In the forming of the organic metal oxide layer, an organic metal oxide film may be formed using a wet coating method, a sputtering method, or a vapor deposition method. As an example, the organic metal oxide film may be a ferrocene film. Preferably, a deposition method such as atomic layer deposition (ALD) or temperature-regulated chemical vapor deposition (CVD) is used, and more preferably, TR-CVD (temperature-regulated chemical vapor deposition) is used. A ferrocene layer can be formed. As an example, when the TR-CVD is applied, the amount of iron oxide deposited on the inorganic oxide can be easily adjusted by adjusting the amount of ferrocene, and the manufacturing process of the photocatalyst can be simplified and the photocatalyst can be efficiently provided.

The step of forming the organic metal oxide layer is performed at room temperature to 120°C, preferably 40°C to 100°C; More preferably it can be carried out at 60 ℃ to 100 ℃. That is, it can be carried out at 60 ℃ to 100 ℃ in order to induce the deposition by the vaporization process of the organic metal oxide layer when applying TR-CVD.

The step of forming the organic metal oxide layer is performed in an air or oxygen atmosphere under atmospheric conditions, and may further include an inert gas.

The forming of the organic metal oxide layer may include ferrocene in an amount of 0.01% to 20% by weight relative to the inorganic oxide, and may form the ferrocene layer.

According to an embodiment of the present invention, the step of forming the metal oxide layer derived from the organic metal oxide is, for example, partially or completely oxidized with a metal oxide through heat treatment of the organic metal oxide layer, carbon residues, etc. The same impurities can be removed.

The forming of the metal oxide layer derived from the organic metal oxide may include 50°C to 900°C; Alternatively 100°C to 800°C; Heat treatment may be performed at two or more stages at a temperature.

For example, the step of forming the ferrocene-derived iron oxide layer includes a first heat treatment at a temperature of 100°C to 300°C and a second heat treatment at a temperature of 300°C to 900°C, and each step is different from each other. It can be heat treated at a temperature. Each of the above steps is performed for 1 minute to 20 hours, respectively, and air, 20% or more; It can be carried out in an air or inert gas atmosphere containing at least 40% oxygen.

That is, the first heat treatment step may be an annealing process for depositing a metal oxide that is converted to a metal oxide by reaction of an organic metal oxide and oxygen. The second heat treatment step is a post-heat treatment step after the first heat treatment step, and may be an annealing process that improves the activity and performance of the photocatalyst by removing impurities such as carbides.

Hereinafter, the present invention will be described in more detail by examples and comparative examples.

However, the following examples are intended to illustrate the present invention, and are merely examples of selecting ferrocene as an organic metal oxide, and the contents of the present invention are not limited to the following examples.

Example 1

By using a TR-CVD (temperature controlled chemical vapor deposition) reactor of Figure 3, and utilizing the temperature controlled chemical vapor deposition method shown in Fig producing a photocatalyst (Fe-TiO ₂₎ of the iron oxide particles in the nano-scale deposited on the TiO ₂ Did. More specifically, 0.02 g of Ferrocene, a precursor of iron, is placed in a container made of quartz on the inner bottom of a reactor made of stainless steel surrounded by a heating band. After placing 3 g of TiO ₂ (TiO ₂ , P-25, Evonik, particle size: 25 nm) in a container made of stainless steel wire in the center inside the reactor, the reactor is sealed with polyimide tape. The temperature of the reactor was carried out by a TR-CVD vaporization process at 60° C. for 2 hours, and then a ferrocene deposition process was carried out, and the temperature was raised to 200° C. and maintained for 12 hours to convert to iron oxide.

Then prepare a final iron oxide -TiO ₂ hybrid photocatalytic nano-structure (or, expressed as Fe-TiO ₂₎ by an additional heat treatment for 2 hours at 750 ℃ in dry air gas atmosphere to remove the TiO _2. The content of iron deposited on TiO ₂ under these conditions is about 0.09 wt%.

Example 2

An iron oxide-TiO ₂ hybrid nanostructured photocatalyst was prepared in the same manner as in Example 1 except that 0.05 g of the iron precursor Ferrocene was applied. The iron content deposited on TiO ₂ under the conditions is about 0.13 wt%.

Example 3

An iron oxide-TiO ₂ hybrid nanostructured photocatalyst was prepared in the same manner as in Example 1, except that 0.1 g of the iron precursor Ferrocene was applied. The iron content deposited on TiO ₂ under the conditions is about 0.65 wt%.

Example 4

An iron oxide-TiO ₂ hybrid nanostructured photocatalyst was prepared in the same manner as in Example 1, except that 0.3 g of the iron precursor Ferrocene was applied. The content of iron deposited on TiO ₂ under these conditions is about 1.81 wt%.

The prepared photocatalyst (Fe-TiO ₂ ) is compared to a TiO ₂ photocatalyst coated with a general iron oxide, and the transparency and color are shown in FIG. 5. 5, the photocatalyst (Fe-TiO ₂ ) coated with ferrocene-derived iron oxide according to the present invention is more transparent and lighter than the photocatalyst (Fe ₂ O ₃ -TiO ₂ ) coated with iron oxide (Fe ₂ O ₃ ). It can be seen that it has a yellow color.

The TEM image (image measured with a transmission electron microscope) of the prepared photocatalyst (Fe-TiO ₂ ) was measured and shown in FIG. 6. 6 shows that as the iron content decreases, the size of the iron oxide particles deposited on the Fe-TiO ₂ surface decreases.

The specific surface area (BET) and BJH average pore size through the nitrogen adsorption analysis of the prepared photocatalyst (Fe-TiO ₂ ) are measured and are shown in Table 1.

0.13 wt% Fe-TiO ₂ 0.65 wt% Fe-TiO2 1.81 wt% Fe-TiO ₂ BET Surface area(m ² /g) 11.6259 10.3426 8.3939 BJHAdsorption average pore size(nm) 13.2 12.5 13.9

Looking at Table 1, it can be seen that even when the iron content of Fe-TiO ₂ is changed, the specific surface area and the average pore size do not change significantly, and the mesopores of Fe-TiO ₂ are formed.

Evaluation Example 1

Put the photocatalyst (Fe-TiO ₂ ) of Example 1 in a volume 5.3 L reactor composed of quartz glass on the top, acetaldehyde initial concentration 66 ppm, dry air (relative humidity: ~33%, total pressure 760 torr) and the photolysis properties of acetaldehyde were analyzed by irradiating the visible light region with white sports flooring at room temperature. Acetaldehyde in the reactor was measured by gas chromatography. The results are shown in FIG. 7.

FIG. 7 is a graph showing (a) acetaldehyde mole number change over time of visible light (white light) irradiation at 33% humidity, and (b) carbon dioxide mole number change as a result of photodecomposition reaction of acetaldehyde. Looking at it, the photocatalyst (Fe-TiO ₂ ) prepared in Example can be confirmed that photodecomposition of acetaldehyde is made by photocatalytic activity by irradiation with visible light (white light), and the ferrocene deposition amount is 0.09 wt% and decomposition efficiency in visible light You can see this is the biggest. In addition, it can be seen that the smaller the iron content, the faster the photodecomposition rate of acetaldehyde of Fe-TiO ₂ .

Evaluation Example 2

The photocatalyst (Fe-TiO ₂ ) having a ferrocene deposition amount of 0.13 wt% was analyzed for the photodegradation properties of acetaldehyde in the same manner as in Evaluation Example 1 under dry conditions without humidity and relative humidity: ~33%. Acetaldehyde and carbon dioxide in the reactor were periodically measured using gas chromatography. The results are shown in FIGS. 8 and 9.

FIG. 8 shows a change in the number of moles of (a) acetaldehyde and (b) the number of moles of carbon dioxide as a result of the photolysis reaction of acetaldehyde according to visible light irradiation time, when the acetaldehyde photolysis experiment was performed under dry conditions and 33% humidity. 7, the slopes of the two graphs were similar in the same acetaldehyde concentration section indicated by a dotted line, and it shows that acetaldehyde photolysis activity remains similar in visible light irrespective of the presence or absence of humidity.

In addition, it can be confirmed that the carbon dioxide generation increases with the light irradiation time, which is generated by the complete oxidation of acetaldehyde.

FIG. 9 shows changes in the number of moles of (a) acetaldehyde and (b) the number of moles of carbon dioxide resulting from the photodecomposition reaction of acetaldehyde according to visible light irradiation time, when repeatedly used in the acetaldehyde photolysis experiment under a 33% humidity condition. It is a graph shown, and it can be seen from FIG. 8 that high photocatalytic activity is maintained even in a repeated photolysis experiment.

Overall, the present invention, TiO ₂ (hereinafter Fe-TiO ₂ ) on which iron oxide is deposited, was utilized for photodegradation experiments of acetaldehyde, which is one of the representative volatile organic compounds, and acetaldehyde photodegradation activity of Fe-TiO ₂ according to the content of iron oxide Compared. As a result, when the iron content was as low as about 0.09 wt%, the photodegradation activity of acetaldehyde of Fe-TiO ₂ was the highest, and about 70% of the initial acetaldehyde concentration (~95 mol ppm) decreased within 20 hours. In addition, although the activity of the photocatalyst is generally affected by humidity, Fe-TiO ₂ prepared in the present invention shows similar catalytic activity under the drying condition and the humidity condition, confirming that the photocatalytic activity is not sensitive to humidity. As a result of nitrogen adsorption experiments of Fe-TiO ₂ having various iron contents, it was confirmed that the iron content did not significantly affect the total specific surface area of the photocatalyst. In addition, considering that the photocatalytic activity of Fe-TiO ₂ was greatly affected by the iron content, it can be seen that the photocatalytic activity is more important in the electronic structure of the interface between the deposited iron oxide nanoparticles and TiO ₂ than the surface structure. . In addition, it was confirmed through a transmission electron microscope that the smaller the iron content, the smaller the size of the iron oxide particles present on the surface. When 1 to 3 nanometer-level iron oxide particles were deposited, the photocatalytic activity may be increased. Based on the results of the analysis, Fe-TiO ₂ absorbs light in the visible region when the iron oxide nanoparticles of a very small size have a content of about 0.09 wt%, and the electron/hole pairs are most efficiently separated, and oxygen/ It can react with water to form radicals, which can rapidly break down acetaldehyde. On the other hand, if the target organic material is not completely oxidized and partially oxidized and remains on the surface of the photocatalyst to block the active site, the activity of the photocatalyst decreases, which has been pointed out as one of the biggest problems of the photocatalyst. However, the Fe-TiO ₂ prepared in the present invention maintained the same catalytic activity even in repeated acetaldehyde photolysis experiments, and thus it was confirmed that there was no problem of catalytic activity deterioration.

As described above, although the embodiments have been described by the limited embodiments and drawings, those skilled in the art can make various modifications and variations from the above description. For example, even if the described techniques are performed in a different order than the described method, and/or the described components are combined or combined in a different form from the described method, or replaced or replaced by another component or equivalent Appropriate results can be achieved. Therefore, other implementations, other embodiments, and equivalents to the claims are also within the scope of the following claims.

Claims (10)

Flat base frame; And
Includes; a shock absorber mounted on one surface of the base frame,
The base frame is formed by dispersing a photocatalyst,
The photocatalyst includes an inorganic oxide and a metal oxide layer derived from an organometallic compound formed on the inorganic oxide and has photoactivity in a visible light region of 400 nm or more,
The metal oxide layer includes ferrocene-derived iron oxide,
The metal oxide layer comprises 0.001 to 10% by weight of iron oxide compared to the inorganic oxide,
The photocatalyst is to have photoactivity under dry conditions of humidity of 30% or less,
Sports flooring comprising a visible light active photocatalyst.
According to claim 1,
The flat base frame,
In the polypropylene-based resin matrix, the photocatalyst is formed by dispersing 1% to 99% by weight,
Sports flooring comprising a visible light active photocatalyst.
According to claim 1,
The flat base frame includes a plurality of drain holes formed by patterning.
Sports flooring comprising a visible light active photocatalyst.
According to claim 1,
The shock absorber,
It comprises at least one selected from the group consisting of polypropylene, polypropethylene, metallocene (Metallocene) and thermoplastic elastomer (TPE),
Sports flooring comprising a visible light active photocatalyst.
According to claim 1,
Further comprising a light-emitting portion provided on the lower portion of the flat base frame,
The light emitting unit is to include an optical fiber, LED, or both,
Sports flooring comprising a visible light active photocatalyst.
delete According to claim 1,
The inorganic oxide is to include at least one selected from the group consisting of oxides containing at least one of Ti, Zn, Al and Sn,
Sports flooring comprising a visible light active photocatalyst.
According to claim 1,
The inorganic oxide does not contain an inorganic oxide containing iron,
In the metal oxide layer, ferrocene deposited on the inorganic oxide is heat-treated,
Sports flooring comprising a visible light active photocatalyst.
According to claim 1,
The metal oxide is to include one or more of the compounds represented by the formula (1),
Sports flooring comprising a visible light active photocatalyst.

[Formula 1]
Me _x O _Y H _Z
(Me is one or more metal elements of groups 1 to 3, X, Y and Z are each selected from 0 to 3, and X and Y are not 0.)
According to claim 1,
The specific surface area of the photocatalyst is 5 (m ² /g) or more, and the average pore size is 50 nm or less,
Sports flooring comprising a visible light active photocatalyst.

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