KR102271170B1 - Acryl based resin composition and acryl based flooring articles manufacturing by using the same - Google Patents

Abstract

The present invention provides an acrylic resin composition, as a resin composition for forming a flooring material or a surface coating layer of the flooring material, which comprises: 100 parts by weight of an acrylic base resin; and 1 to 5 parts by weight of a photocatalyst including an inorganic oxide and a ferrocene-derived iron oxide layer formed by doping with ferrocene. In addition, the present invention provides a hard coat flooring material that is manufactured or constructed by the acrylic resin composition, and can basically exhibit air purification properties, heat shielding properties, and anti-slip properties.

Description

Acrylic-based resin composition and acrylic flooring prepared thereby {ACRYL BASED RESIN COMPOSITION AND ACRYL BASED FLOORING ARTICLES MANUFACTURING BY USING THE SAME}

The present invention relates to a flooring material technology, and more specifically, to a material technology of a hard coat flooring material that can be applied to flooring materials such as sports facilities and indoor facilities.

In general, a hard coat used as a flooring material such as a tennis court is mainly manufactured using an acrylic resin as a base resin. These acrylic flooring materials have been manufactured by applying and curing the acrylic resin composition including various functional additives in order to improve various physical properties.

However, it is still necessary to develop additional acrylic flooring materials to improve physical properties, such as durability degradation due to long-term use and surface scratches. In addition, since it is generally installed in sports facilities, it is judged that it is necessary to introduce additional functionality in accordance with this purpose.

An object of the present invention is to provide an acrylic resin composition having excellent air purification properties, self-heating properties, anti-slip properties and durability as an invention considered for the introduction of improvements and additional functions of the above-mentioned acrylic flooring materials.

In addition, an object of the present invention is to provide an acrylic flooring material manufactured by the acrylic resin composition, in which the scratch resistance of the inner surface as well as the above-described properties is remarkably enhanced.

The acrylic resin composition according to an embodiment of the present invention is a resin composition for forming a flooring material or a surface coating layer of the flooring material, comprising: 100 parts by weight of an acrylic base resin; and 1 to 5 parts by weight of a photocatalyst including an inorganic oxide and a ferrocene-derived iron oxide layer formed by doping with ferrocene.

The photocatalyst may include a compound represented by the following Chemical Formula (1).

In the above formula, X and Y are real numbers from 1 to 3, and Z is a real number from 0 to 3.

The acrylic resin composition may further include 0.1 to 5 parts by weight of heat-treated mineral particles extracted by melting and cooling the crushed basalt powder at a temperature of 800° C. to 1000° C., which is below the complete melting temperature.

The inorganic oxide may be an inorganic oxide containing an element such as Ti, Zn, Al, or Sn.

The acrylic resin composition may further include 0.1 to 1.0 parts by weight of a Hindered Amine Light Stabilizer (HALS)-based UV stabilizer based on 100 parts by weight of the composition in the composition.

An acrylic flooring material according to an embodiment of the present invention comprises: a first pellet made of an acrylic resin; And it may be formed by melting the second pellet containing the photocatalyst including the acrylic resin and the inorganic oxide and the ferrocene-derived iron oxide layer formed by ferrocene doping, and applying it to the construction surface and curing it.

The acrylic flooring material may include heat-treated mineral particles extracted by melting and cooling the crushed basalt powder at a temperature of 800°C to 1000°C, which is below the complete melting temperature.

The acrylic flooring material produced by the acrylic resin composition according to the present invention has excellent air purification properties, heat shielding properties, and anti-slip properties due to the photocatalyst. Furthermore, the acrylic resin composition has excellent tensile and elongation properties at the same time, thereby enabling the construction of a flooring material with very improved durability.

The acrylic flooring material of the present invention has excellent heat shielding properties, and by being applied to the hard cord construction of a tennis court, it is possible to effectively suppress an excessive increase in the floor surface temperature due to solar heat.

In addition, the acrylic flooring material of the present invention contains heat-treated mineral particles derived from basalt, so that the scratch resistance of the floor surface can be significantly improved, and in addition to the antibacterial property by the photocatalyst, antibacterial power by far-infrared emission can be additionally provided have.

Furthermore, the acrylic flooring material does not cause a change in the physical properties of the floor surface even after long-term use due to its excellent high weather resistance even when it is installed outdoors.

1 is a flowchart conceptually showing a method for manufacturing heat-treated mineral particles according to an embodiment of the present invention.

Hereinafter, the acrylic resin composition according to an embodiment of the present invention will be described in detail with reference to the accompanying drawings. In addition, the acrylic flooring manufactured thereby will be described in detail. The following descriptions are exemplary descriptions for concretely explaining the technical idea of the present invention, and the technical idea of the present invention is not limited by the following description. It is natural that various embodiments other than the following description are possible, and the technical spirit of the present invention can only be interpreted and limited by the claims described below.

On the other hand, the acrylic resin composition is melt-coated to form a flooring material, so that the active ingredients may be separated and distributed into a plurality of pellets, and the formulation of the resin composition is not significantly limited.

The acrylic resin composition includes an acrylic resin as a base resin and a photocatalyst and heat-treated basalt-derived mineral particles as active ingredients.

Hereinafter, a photocatalyst as one of the active ingredients will be described in detail. The photocatalyst may include: an inorganic oxide including at least one selected from the group consisting of oxides including at least one of Ti, Zn, Al and Sn; and a photocatalyst particle composed of; and a ferrocene-derived iron oxide layer formed on the inorganic oxide. The photocatalyst particles may include an inorganic oxide and a ferrocene-derived iron oxide layer formed by a ferrocene doping process. The ferrocene-derived iron oxide layer is formed as a coating layer on the inorganic oxide, and may improve light absorption and photocatalytic efficiency in a visible ray region.

The inorganic oxide may be an inorganic semiconductor compound exhibiting catalytic activity by absorbing light energy. For example, it is an oxide containing at least one selected from the group consisting of Ti, Zn, Al, Fe, W, Sn, Bi, Ta, Cu, Si, Ru, Sr, Ba and Ce, preferably Ti, Zn , Al and Sn. Specifically, it may be TiO2, Al2O3, ZnO2, ZnO, SrTiO3, Fe2O3, Ta2O5, WO3, SnO2, Bi2O3, NiO, Cu2O, SiO, SiO2, MoS2, InPb, RuO, CeO2, or the like. In addition, a semiconductor compound such as CdS, GaP, InP, GaAs, or InPb may be further included in addition to the oxide. The content of iron in the ferrocene-derived iron oxide layer may be 0.001 to 10% by weight compared to the inorganic oxide.

The ferrocene-derived iron oxide layer may be a heat treatment of ferrocene deposited on the inorganic oxide.

The inorganic oxide includes at least one selected from the group consisting of beads, powders, rods, wires, needles and fibers, and the size of the inorganic oxide is 1 nm or more; more than 10 nm; 30 nm to 500 μm; 30 nm to 100 μm; or 30 nm to 1 μm. The size may mean a diameter, thickness, length, etc. depending on the shape.

The ferrocene-derived iron oxide layer is formed by a ferrocene doping process. For example, the ferrocene layer formed on the inorganic oxide may be thermally decomposed to thermally decompose, and iron oxide converted from ferrocene by the thermal decomposition process may be included. The ferrocene doping process will be described in more detail in the following manufacturing method.

The ferrocene-derived iron oxide is an iron oxide derived from at least one of ferrocene and a ferrocene derivative, and the ferrocene derivative includes a ferrocene aldehyde, a ferrocene ketone, a ferrocene carboxylic acid, a ferrocene alcohol, a phenol or ether compound, a nitrogen-containing ferrocene compound, Sulfur-containing ferrocene compound, phosphorus-containing ferrocene compound, silicon-containing ferrocene compound, 1,1'-di-copper ferrocene, ferrocene boric acid, ferrocenyl Q It may include at least one selected from the group consisting of ferrocenyl cuprous acetylide and bisferrocenyl titanocene.

The content of iron in the ferrocene-derived iron oxide layer 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 may be included. When included within the above range, it is possible to increase the photocatalytic activity in the visible light region to improve the photolysis efficiency. In addition, when the content of iron increases, absorption in the visible region may increase, but since a decrease in photocatalytic activity may occur due to such an increase in the iron content, it is preferable to include the iron content within the above range, and more preferably, The content of iron may be 0.01 to 1% by weight.

The ferrocene-derived iron oxide layer is 0.01 nm or more; 0.1 nm or greater; more than 10 nm; Or it may have a thickness of 1 nm to 100 nm. When included in the above thickness range, it is possible to prevent a decrease in the porosity of the photocatalyst according to the increase in the thickness of the coating layer, and to increase the amount of moisture, OH- ions, decomposition target, etc. adsorbed to the surface to improve the photolysis performance. In addition, the ferrocene-derived iron oxide layer is 0.01 nm or more; 0.1 nm or greater; more than 10 nm; Or it may include a ferrocene-derived iron oxide having a size of 1 nm to 100 nm. The size may mean length, diameter, thickness, etc. depending on the shape. The ferrocene-derived iron oxide may include at least one of compounds represented by the following Chemical Formula 1.

[Formula 1]

In the above formula, X and Y are real numbers from 1 to 3, and Z is a real number from 0 to 3.

That is, the photocatalyst absorbs light in the visible light region and introduces iron oxide (FexOyHz), a stable and inexpensive semiconducting material, to the TiO2 surface in the form of nano-sized particles to form photocatalytic particles that respond to visible light. .

The photocatalyst particles may have photoactivity in one environment of a visible light region condition of 400 nm or more, a dry condition of 30% or less humidity, or both.

The photocatalyst particles absorb light so that the wavelength region showing the photoreaction is extended from the ultraviolet to the visible ray region, and in particular, it may exhibit excellent photocatalytic activity in the visible ray region of 400 nm or more. In addition, the photocatalytic reactivity capable of adsorbing and decomposing the decomposition target on the surface is improved, so that it has photocatalytic activity in various humidity ranges, and can exhibit excellent photocatalytic activity even in dry conditions of 30% or less of humidity.

The photocatalyst particles are 5 (m2/g) or more; 5 (m2/g) to 1000 (m2/g); or a specific surface area of 5 (m2/g) to 100 (m2/g), and an average pore size of 50 nm or less. That is, by introducing ferrocene-derived iron oxide to the surface, the adsorption amount of the decomposition target on the surface of the photocatalyst increases, and the photolysis reactivity can be increased to improve the efficiency of the photocatalyst.

The inorganic oxide-based photocatalyst is applied to the decomposition of various harmful substances, that is, it can be used to treat 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 can 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, acid and basic gas, acetaldehyde, VOC (Volatile Organic Compounds) such as ketones, aromatic hydrocarbons and aliphatic hydrocarbons (Paraffin-based and Olefin-based) hydrocarbons, ozone gas, organic and inorganic glass gas, and more specifically, carbon dioxide, carbon monoxide, NOx, SOx, HCl, HF, NH3, methylamine, formaldehyde, hydrogen sulfide, amine, methylmergaptan, hydrogen, oxygen, nitrogen, methane, paraffin, olefins or the like. Examples of the liquid include formaldehyde, acetaldehyde, benzene, toluene, MEK (Methyl Ethyl Ketone), trichloroethylene, disinfectant, gasoline, diesel, oil, alcohol, Phenol, dye, and the like, and the solid may include, but is not limited to, transition metals, noble metals such as Pt and Pd, ions and/or particles such as Hg and Cr, and nanoparticles of 100 nm or less.

forming a ferrocene layer on an inorganic oxide to prepare the photocatalyst; and heat-treating the inorganic oxide on which the ferrocene layer is formed to form a ferrocene-derived iron oxide layer.

The inorganic oxide may be prepared by preparing an inorganic oxide dispersion or coating an inorganic oxide on a substrate. The dispersion is an aqueous solvent, an oily solvent, or a mixture of both, and the substrate may be a silicon substrate, a wafer, a glass substrate, a semiconductor substrate, a metal substrate, or 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 ferrocene layer, a ferrocene layer may be formed using a wet coating method, a sputtering method, or a deposition method. Preferably, a deposition method such as ALD (atomic layer deposition) or CVD (temperature-regulated chemical vapor deposition) is used, and more preferably, TR-CVD (temperature-controlled chemical vapor deposition) is used. A ferrocene layer can be formed. When TR-CVD is applied, the amount of iron oxide deposited on the inorganic oxide can be easily controlled by controlling the amount of ferrocene, and the photocatalyst can be manufactured by simplifying the manufacturing process and efficiently.

The step of forming the ferrocene layer is carried out at room temperature to 120 °C, preferably 40 °C to 100 °C; More preferably, it may be carried out at 60 °C to 100 °C. That is, when TR-CVD is applied, it may be carried out at 60° C. to 100° C. in order to induce deposition by the vaporization process of ferrocene. The forming of the ferrocene layer may be performed in an air or oxygen atmosphere under atmospheric conditions, and may further include an inert gas. In the forming of the ferrocene layer, the ferrocene layer including 0.01 wt% to 20 wt% of ferrocene relative to the inorganic oxide may be formed.

According to an embodiment of the present invention, in the forming of the ferrocene-derived iron oxide layer, the ferrocene layer may be partially or completely oxidized to iron oxide through heat treatment, and impurities such as carbon residues may be removed. The step of forming the ferrocene-derived iron oxide layer, 50 ℃ to 900 ℃; or 100°C to 800°C; It can be heat treated in two or more steps at a temperature. For example, the step of forming the ferrocene-derived iron oxide layer comprises the step of performing 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, each step being different from each other It can be heat treated at high temperature. Each of the above steps is carried out for 1 minute to 20 hours, respectively, in air, 20% or more; It may be carried out in an air or inert gas atmosphere containing 40% or more oxygen. That is, the first heat treatment may be an annealing process for depositing iron oxide that is converted into iron oxide by reaction of ferrocene and oxygen. The second heat treatment step is a post heat treatment step after the first heat treatment step, and may be an annealing step for improving the activity and performance of the photocatalyst by removing impurities such as carbides.

The thus-prepared photocatalyst may be included in the total resin composition so as to be 1.0 to 5 parts by weight based on 100 parts by weight of the base resin.

The type of the base resin is an acrylic resin, and resins having various known molecular weights and physical properties are used, but may be variously selected in consideration of the construction purpose, use, and the like.

Meanwhile, the acrylic resin composition may include heat-treated mineral particles derived from basalt in order to strengthen physical properties. The heat-treated mineral particles are preferably used in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the acrylic resin.

In this embodiment, the heat-treated mineral particles are particles extracted by melting and cooling the crushed basalt powder under a temperature of 800°C to 1000°C, which is 1400°C or less, which is a complete melting temperature. The melting temperature is an important factor for expressing the physical properties of the heat-treated mineral particles, and if the melting step is performed outside the temperature conditions or at a normal basalt melting temperature, the object of the present invention cannot be achieved.

Hereinafter, the step of preparing the basalt-derived heat-treated mineral particles will be described in detail.

1 is a flowchart conceptually showing a method of manufacturing heat-treated mineral particles according to an embodiment of the present invention.

Referring to FIG. 1 , for the production of heat-treated particles derived from basalt (S100), basalt preparation and washing step (S110) of preparing and washing basalt is first performed. The basalt sample is a commercially purchased sample, and there is no particular limitation in shape. However, in order to control the particle size of the subsequent crushing step, it is preferable not to purchase a powdered sample as the basalt sample. Washing is a measure that preemptively removes impurities present on the surface of basalt so that it cannot act as a factor that changes the temperature of the melting stage in the future. As the method for removing impurities, a method using a specific gravity difference or the like may be used.

After the basalt is washed and dried, the basalt crushing step (S120) is performed. Basalt crushed material is prepared through the crushing step (S120), and crushing is preferably performed so that the average particle diameter of the crushed material particles is maintained at a level of about 0.1 mm to 0.5 mm. For melting efficiency, it is advantageous to crush basalt more finely, but if the average particle diameter of the crushed particles is less than 0.1 mm, melting occurs too rapidly and it may be difficult to express complete properties according to abnormal heat treatment. In the basalt crushing step (s120), the crushed foreign substances included in the basalt are separated in various ways. This is because foreign substances may cause abnormality of the melting temperature of the melting step (S130), which will be described later.

When the crushed basalt is prepared, a low-temperature melting step (S130) of heating and melting the crushed basalt is performed. The crushed basalt should be melted in a relatively low temperature environment of 800 to 1000 ° C rather than a temperature of 1400 ° C or higher, which is a typical complete melting temperature, and by melting under the temperature, useful properties for the floor material can be achieved.

Meanwhile, in the process of performing the melting step (S140), sulfur or an acidic solution may be added.

When the low-temperature melting step (S130) is completed, a cooling step (S140) of cooling the melt is performed. The cooling should be sufficiently performed at room temperature. When the cooling step (S1040) is completed, by performing the powdering step (S150) of pulverizing the cooled melt, basalt-derived heat treatment mineral particles according to an embodiment of the present invention can be prepared.

Meanwhile, the heat-treated mineral particles may be prepared in the form of pellets mixed with an acrylic resin and melted in a melting process for final flooring construction. The heat treatment mineral particles are test results (Korea Institute of Materials) SiO ₂ 100 parts by weight; Al ₂ O ₃ 25 to 32 parts by weight; 18 to 22 parts by weight of CaO; 18 to 22 parts by weight of MgO; Fe ₂ O ₃ 18 to 22 parts by weight; and metal components such as Ti, Y, La, Ce and Nd.

Table 1 below is a table illustrating the composition of the heat-treated mineral particles.

SiO ₂ Al ₂ O ₃ CaO MgO Fe ₂ O ₃ Ti Y La Ca Nd bal 15.33 10.19 10.07 10.18 1.19 0.0043 0.0095 0.0131 0.0071

The heat-treated mineral particles have a scratch strength of at least 9.0H and a Mohs hardness of at least 7.3 when directly melt-coated on the surface of the base material, and can form a coating film without peeling and breaking phenomena under a temperature of 500°C and -70°C, respectively. It is a material with physical properties.

On the other hand, the acrylic resin composition may further include 0.1 to 1.0 parts by weight of a HALS (Hindered Amine Light Stabilizer)-based UV stabilizer relative to 100 parts by weight of the composition in the composition to enhance weather resistance. The UV stabilizer makes it possible to minimize cracks or property changes in the surface state as much as possible even when the flooring material is used outside for a long time.

The composition prepared as above is preferably understood as a composition in a molten state for flooring construction. For actual flooring construction, each active ingredient such as base resin pellets, photocatalyst + base resin pellets, heat treatment mineral particles + base resin pellets, UV stabilizer + base resin pellets, etc. can be distributed in the form of pellets.

In addition, the configuration of the pellet is not limited to the above example, it can be variously modified.

By melting these pellets at the flooring construction site and applying them on the base layer, an acrylic flooring material according to an embodiment of the present invention can be constructed. In addition, the flooring material itself may form the body of the floor, but may also be constructed in the form of a coating layer on a pre-formed floor surface.

Currently, the physical properties of the acrylic resin of the present invention have been provided with various experimental data from various experimental institutions, and attachments are omitted in this specification, but will be submitted if necessary during the examination of the present application in the future.

Claims (7)

A composition comprising 100 parts by weight of an acrylic base resin, 1 to 5 parts by weight of a photocatalyst, and 0.1 to 5 parts by weight of heat-treated mineral particles,
The photocatalyst includes an inorganic oxide and a ferrocene-derived iron oxide layer formed by ferrocene doping on the inorganic oxide,
The heat-treated mineral particles are extracted by melting and cooling the crushed basalt powder under a temperature of 800 ° C to 1000 ° C, which is below the complete melting temperature,
An acrylic resin composition for forming a flooring material or for forming a flooring surface coating layer.
According to claim 1,
The ferrocene-derived iron oxide layer is an acrylic resin composition comprising at least one selected from the compounds represented by the following formula (1).
[Formula 1]

(In the above formula, X and Y are real numbers from 1 to 3, and Z is a real number from 0 to 3.)
delete According to claim 1,
The inorganic oxide is an acrylic resin composition comprising at least one element selected from the group consisting of Ti, Zn, Al and Sn.
According to claim 1,
The acrylic resin composition, the acrylic resin composition, characterized in that it further comprises 0.1 to 1.0 parts by weight of a HALS (Hindered Amine Light Stabilizer)-based UV stabilizer relative to 100 parts by weight of the composition in the composition.
Pellets made of an acrylic resin; Pellets containing an acrylic resin and a photocatalyst; And after mixing and melting the pellets containing the acrylic resin and heat-treated mineral particles, as a flooring formed by applying and curing the construction surface,
The photocatalyst includes an inorganic oxide and a ferrocene-derived iron oxide layer formed by ferrocene doping on the inorganic oxide,
The heat-treated mineral particles are extracted by melting and cooling the crushed basalt powder under a temperature of 800 ° C to 1000 ° C, which is below the complete melting temperature,
Acrylic flooring. delete

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