KR20240063233A - A Photocatalyst Coating Material and An Ionizer Apparatus Using That - Google Patents

Abstract

The present invention relates to a photocatalyst coating composition and an ionizer device using the same. The photocatalyst coating composition includes a photocatalyst mixed with 1 part by weight of silver phosphate and 9 parts by weight of titanium phosphate, a siloxane-based polyol, an ether-based polyol, and a perfluorine-based additive. It is characterized in that it contains a binder composition to be mixed, and the perfluorinated additive is, after reacting butylacrylate, a surfactant and an initiator, butylacrylate, glycidyl methacrylate, perfluoroalkyl ethyl acrylate, It is characterized in that it is manufactured by adding an initiator and sodium sulfate to react.

Description

Photocatalyst coating composition and ionizer apparatus using the same {A Photocatalyst Coating Material and An Ionizer Apparatus Using That}

The present invention relates to a photocatalyst coating composition and an ionizer device using the same, and more specifically, to a photocatalyst coating composition that minimizes ozone generation and an ionizer device using the same.

Recently, due to the influence of bacterial-viral diseases such as super bacteria, new flu, and COVID-19, concerns about respiratory diseases, asthma, and atopy are spreading nationwide. As the desire for a comfortable living environment is increasing, antibacterial, There is a demand for the development of products with sterilizing functions. In addition, most plastic products with antibacterial function are products with a chemically synthesized antibacterial coating applied to the surface, and there are problems with the harmfulness to the human body and the antibacterial lifespan, so a principled alternative is required.

As indoor air quality has become increasingly important to society, the Ministry of Environment is making efforts to enact indoor air quality management laws and establish management systems. Bio aerosols and volatile organic compounds, which are indoor pollutants, are being removed worldwide. There is an urgent need for the development of eco-friendly antibacterial and antifungal products, with the main research targets being organic compounds (VOCs) and fine dust (nanoparticles).

To this end, it is an environmental technology related to low-carbon green growth, an environmental (ET)-based technology that combines IT & NT & BT, a passive sterilization technology with antibacterial and anti-fungal properties, and an active sterilization technology that applies functional plastic and plasma sterilization system technology. Econizer technology appeared.

Plasma is used in the economizer, and when plasma is generated, high voltage is applied to microorganisms such as bacteria, causing dislocations inside and outside the cell membrane, which destroys the cell membrane or causes (+) ion clusters and hyperactivity around microbial contaminants such as bacteria/viruses. When (-)ion clusters collide, `OH radicals are generated in the energy, and the generated radicals combine with H+ ions inside microorganisms and are ultimately oxidized into harmless water.

However, the prior art had the following problems.

When applying plasma technology, the number of ions is generated exponentially as (+) ions and (-) electrons are generated rapidly around the electrode, and there is a disadvantage in that ozone and radicals are simultaneously generated depending on the size of the voltage.

Registered Patent No. 10-2222573

In order to solve the above-mentioned problems, the purpose of the present invention is to provide a photocatalyst coating composition by formulating a titanium dioxide-based photocatalyst that minimizes ozone generation.

Another object of the present invention is to provide an ionizer device using a photocatalyst coating that minimizes ozone generation and has high durability and an antibacterial plastic material.

In order to achieve the above-described object, the composition of the photocatalyst coating agent of the present invention is a binder composition in which a photocatalyst mixed with 1 part by weight of silver phosphate and 9 parts by weight of titanium phosphate, a siloxane-based polyol, an ether-based polyol, and a perfluorine-based additive are mixed. It is characterized by including.

The perfluorinated additive is produced by reacting butylacrylate, a surfactant, and an initiator, and then adding butylacrylate, glycidyl methacrylate, perfluoroalkyl ethyl acrylate, an initiator, and sodium sulfate. Do it as

An ionizer device using a photocatalyst coating composition, which is another embodiment of the present invention, includes an ionizer electrode portion, an ionizer module portion on which various components that control the ionizer electrode portion are mounted, the ionizer electrode portion, and the ionizer module. It includes an ionizer housing part with a space formed therein to accommodate the unit, and the photocatalyst coating composition described above is applied to the surface of the ionizer module part.

The ionizer housing part is characterized in that it contains a material coated with oyster shell membrane powder with silane or fatty acid salt.

The ionizer housing part is characterized in that it contains a material made by coating oyster shell powder with silane or fatty acid salt on polypropylene polymer or ABS polymer.

The photocatalyst coating composition according to the present invention and the ionizer device using the same have the following effects.

The titanium dioxide-based photocatalyst is safely fixed even under the operating and use environment conditions of the ionizer, and the ionizer housing also has an increased antibacterial function, which has the advantage of improving durability and use environment.

Figure 1 is a block diagram showing a preferred configuration of an ionizer device using the photocatalyst coating composition according to the present invention.
Figure 2 is a diagram showing the reaction mechanism of the photocatalyst used in the present invention.
Figure 3 is a diagram showing electrical conductivity according to the type of photocatalyst used in the present invention.
Figure 4 is a diagram showing the stability of the photocatalyst coating composition according to the present invention.
Figure 5 is a diagram showing the reaction mechanism of WPU applied with Siloxane + Ether-based polyol, which constitutes the binder of the photocatalyst coating agent according to the present invention.
Figure 6 is a diagram showing the WPU manufacturing process using the perfluoroacryl additive that constitutes the binder of the photocatalyst coating agent according to the present invention.
Figure 7 is a diagram showing the test results of an antibacterial plastic material (PP-based) of the housing portion of an ionizer device using the photocatalyst coating composition of the present invention.
Figure 8 is a diagram showing the test results of an antibacterial plastic material (ABS type) of the housing portion of an ionizer device using the photocatalyst coating composition of the present invention.

Hereinafter, preferred embodiments of the photocatalyst coating composition according to the present invention and an ionizer device using the same will be described in detail with reference to the attached drawings.

The ionizer device of the present invention includes an ionizer electrode unit 10 that generates plasma ions, an ionizer module unit 20 on which various components that control the ionizer electrode unit 10 are mounted, and the ionizer electrode unit. (10) and an ionizer housing portion 30 with a space formed therein to accommodate the ionizer module portion 20.

The ionizer device is provided with an ionizer electrode unit (10). The ionizer electrode unit 10 may have a discharge needle-ground ring type structure. The material of the discharge needle may be silver (Ag) or gold (Au).

The ionizer electrode unit 10 is provided with an ionizer module unit 20. In order to generate plasma discharge in the ionizer electrode unit 10, a high voltage generation circuit is provided.

The circuit of the ionizer module unit 20 is generally provided on a PCB substrate, and the PCB substrate is coated with the photocatalyst coating composition according to the present invention. The photocatalyst coating composition can minimize the generation of ozone when a plasma phenomenon occurs.

Then, the ionizer housing portion 30 is provided. The ionizer housing portion 30 is provided with a space inside so that the ionizer electrode portion 10 and the ionizer module portion 20 are mounted in the inner space.

The ionizer housing part 30 may be made of a plastic material, and may be made of an antibacterial plastic material to prevent contamination by the ionizer housing part 30.

First, the photocatalyst coating composition for coating the ionizer module portion will be described.

One of the most widely used materials in photocatalytic reactions is titanium dioxide (TiO ₂ ). TiO ₂ has already been widely used in the water splitting process (hydrogen production) of photoelectrochemistry and is known to have an appropriate band gap energy and excellent chemical stability. Materials that can be used as photocatalysts other than TiO ₂ include V ₂ O ₅ , ZnO, Fe ₂ O ₃ , and WO ₃ . Among these, Kawaguchi and Uejima2 decomposed phenol using ZnO suspension. In addition, ZnO is greatly affected by the pH of the solution and has the disadvantage that in strongly acidic solutions, Zn ions dissolve and its catalytic properties disappear. In addition, photodecomposition research using catalysts such as Fe2O3 and V2O5 is in progress, but no material with photocatalytic activity comparable to TiO ₂ has been reported yet.

Among these various types of metal oxides, transition metal oxides composed of d-orbitals with partially filled electrons are useful for use as photocatalysts. When metal oxide catalysts absorb light energy of a wavelength equal to or higher than the bandgap energy they possess on their surface, the valence band filled with electrons changes from the valence band filled with electrons to the conduction band with empty electrons. It is caused by moving to the conduction band and forming an electron (e-)-hole (h+) charge-separated pair between the valence band and the conduction band, forming a space charge region.

If the electron-hole pairs formed in this way do not participate in each oxidation-reduction reaction, recombination occurs at the speed of nano seconds as shown in equation (1), generating energy as heat or light.

TiO ₂ + hν → TiO ₂ (e-CB + h+ VB) Equation (1)

TiO ₂ (e-CB + h+VB) → heat equation (2)

The two generated charge carriers (e- or h+) diffuse very quickly toward the surface of the particle, and the conduction band electrons are captured on the Ti(IV) surface (Equation (3)) or by interfacial electronic transition (Equation (4)). The reaction proceeds by an acceptor (Aads).

Ti(IV)surface + e-CB → Ti(Ⅲ)surface Equation (3)

Aads + e-CB → A·-ads equation (4)

O2ads + e-CB → O2ㆍ-ads Equation (5)

And the valence band hole can be captured by the intrinsic oxygen site equation (6) and the donor (Dads) adsorbed on the particle surface as shown in equation (7).

Ti(IV)-O ₂ -Ti(IV) + h+VB → [Ti(IV)-O·--Ti(IV)] Formula (6)

Dads + h+VB → D·+ads Equation (7)

The trapping of holes on the surface of very strongly hydrated and hydroxylated TiO ₂ particles results in surface binding of OH·+ (Equation (8)).

Ti(IV)surface-OH + h+VB → Ti(IV)surface-OH·+ Formula (8-a)

Ti(IV)surface-OH2+ + h+VB → Ti(IV)surface-OH·+ + H+aq. Equation (8-b)

Ti(IV)surface-OHㆍ+ + D → Ti(IV)surface + Dㆍ+-OH Equation (9)

On the other hand, oxygen molecules (O2) act as acceptors of electrons adsorbed on the catalyst surface, creating superoxide radical anions (Equation (5)), and also serve as oxidizers for metal cations and other organic substances or oxidize water. This produces hydrogen peroxide (H ₂ O ₂ ). The excited catalyst undergoes an oxidation reaction with hydroxy ions in the aqueous solution adsorbed on its surface, generating OH radicals, a powerful oxidizing agent. These OH radicals induce a decomposition reaction of organic substances. The lifespan of the charge-separated pair formed by such irradiation of light is the time required for the electrons moving to the conduction band to be transferred to the adsorbed acceptor, and the time for the holes formed in the valence band to be transferred to the donor adsorbed on the surface. It should be long enough to allow enough time to develop. For this reason, when using sunlight or a light source capable of irradiating similar wavelengths as a driving force for the photodecomposition reaction, the band gap energy and charge separation behavior to be considered must be understood in order to select the optimal photocatalyst.

Among the photocatalysts shown in Figure 3, there are several types of semiconductor materials that can be used as photocatalysts, but among these, titanium dioxide (TiO ₂ ) is receiving the most attention. The main reason is its chemical stability, which prevents it from being corroded by most acids, bases, and organic solvents. Zinc oxide (ZnO) has an energy band structure similar to titanium dioxide and is reported to be highly active as a photocatalyst. However, when ZnO is irradiated with light in an aqueous solution, it melts as Zn2+ (photodissolution). It is easily soluble in common acids such as hydrochloric acid and nitric acid. Metal sulfides and metal chalcogenites use visible light, but when most of them, like ZnO, are used as photocatalysts in water, the metals dissolve in water in the form of ions. CdS or GaP can absorb a large portion of sunlight, but are known to lose stability after repeated experiments (eg. CdS+2h+→Cd2++S). In addition, Cd, Se, As, etc. are known to be toxic. In addition, TiO ₂ has strong oxidizing power, low cost, is non-toxic and non-carcinogenic, and is harmless to the human body, making it a suitable material for use as a photocatalyst.

Next, the photocatalyst coating composition will be described.

First, the photocatalyst in the present invention is to develop a visible light catalyst that can achieve a 40-50% reduction in price competitiveness while securing the same performance as the previously developed photocatalyst with a synthesis ratio of silver phosphate and titanium dioxide of 5:5. The visible light catalyst of the present invention refers to a visible light catalyst in which the synthesis ratio of silver phosphate (Ag ₃ PO ₄ ) and titanium dioxide (TiO ₂ ) is 1:9.

go. Selection of potential and probable factors

In the present invention, the type of heavy metal catalyst and the amount of metal catalyst added were selected as potential factors (Pre_CTQ), and among the potential factors X, temperature and humidity, which are the catalytic activity environment, were selected as fixed factors. The temperature range was fixed at ±25±5℃ and the relative humidity was fixed at 55±15%. The additive metal catalyst group A was made of 4-period transition metals, group B was made of noble metals, and group C was made of alkali metals. In addition, the light source condition was fixed to fluorescent lamps and the intensity was tested in the range of 1300 to 1400 lx. As a result of preliminary review of the present invention, the cost of photocatalyst coating was fixed at 1:9 for the mixing ratio of silver phosphate and titanium dioxide in order to reduce the cost of the developed photocatalyst to 40-50% of the existing level.

me. DOE analysis for selection of fatal factors (main effect analysis)

As a result of DOE analysis, the fatal factor for methylene blue decomposition performance (P-value〈0.05) or less is the type of metal catalyst (P=0.000) and the amount added (P=0.000). As a result of the main effect analysis, Mn addition < Pt addition, low concentration > high concentration. The results of the ANOVA analysis and Pareto chart analysis were analyzed as the main factors of the type of metal catalyst and the amount of metal catalyst added, CTQ.

all. Precious metal catalyst selection (screening test)

As a result of examining noble metal metal catalysts, when platinum (Pt) and gold (Au) were added as a photocatalyst (synthesis ratio of silver phosphate and titanium dioxide of 1:9), the decomposition performance was about 35-36%, but palladium (Pd) showed a decomposition performance of about 35-36%. ), it was analyzed that there was no increase in efficiency due to addition. In addition, when a visible light photocatalyst was synthesized by adding a nano particle process of a metal catalyst, the performance was improved by about 4 to 5%. In a methylene blue decomposition experiment, 1 g of visible light catalyst was mixed with 50 g of methylene blue solution, stirred, and the amount of light was measured using a visible light source. Absorbance was measured at 1350±50lx. The absorbance meter used at this time was measured using Simadzu UV-1800.

[Performance evaluation of photocatalyst coating]

go. Stability evaluation of photocatalytic coatings

Since changes over time at room temperature must be evaluated over a long period of time, we attempted to evaluate the stability of the coating solution by conducting a severe test of the coating solution. For liquid stability, the prepared coating liquid was sampled in a 60 ml container and stored in an oven at 60°C to observe changes in the liquid over time. As shown in Figure 4, after 1 day at 60°C, it is considered to be stable at room temperature for 1 to 2 months, and after 2 days at 60°C, it is thought to be stable at room temperature for about 2 to 4 months. It was judged to be stable for about 5 to 6 months at room temperature after 3 days at 60 ℃, and the liquid stability standard was judged to be excellent if it showed stability at 60 ℃ for more than 3 days.

me. Chemical resistance test of photocatalyst coating agent

To evaluate the chemical resistance of the coated specimen, the coated specimen is placed in a solution prepared with 5% Na ₂ CO ₃ and 5% CH ₃ COOH, the coated specimen is immersed by more than 50%, and left in an atmosphere at room temperature for 24 hours. . After the test, take out the specimen and wash it with running water to evaluate swelling and discoloration of the coating film.

all. Comparative evaluation of performance according to photocatalyst thin film coating thickness

The prepared photocatalyst coating solution is uniformly coated on the plate PCB electrode area excluding the high voltage electrode area of the ion generating electrode using a screen printing method. The evaluation of adhesion performance according to thin film thickness was conducted primarily by evaluating the appearance, observing the adhesion of foreign substances and the phenomenon of the coating thin film detaching from the PCB electrode surface, and recovering and analyzing the components detached from the electrode surface.

In the present invention, it is preferable to measure the thin film before and after coating, but here, the number of coatings was performed from 1 to 3 times and the state of the coating film was observed. As shown in the table below, when coated once, it was confirmed that the thin film was coated thinly and uniformly with a thickness of approximately 9 to 11 um. The table below shows the final results according to the coating thickness.

Thin film thickness (㎛) Coating Recovery note 10 1 time No thin film detachment observed from the surface (less than 1%) 20 Episode 2 Some thin film detachment phenomenon observed (less than 10%) 30 3rd time Thin film detachment phenomenon of more than 20%

Next, the production of the binder for photocatalyst will be described.

To develop a water-dispersed polyurethane resin for photocatalyst binder, synthesis experiments were conducted for each type of polyol (Ether-based, Ester-based, Carbonate-based, Siloxane-based) and composition ratio, and their characteristics were examined.

A. Manufacturing of WPU using Siloxane + Ether polyol

① Reaction raw materials

In this experiment, poly(dimethylsiloxane), hydroxy terminated (#550), a siloxane polyol, and poly(dimethylsiloxane), bis(hydroxyalkyl) terminated (#5,600) were mixed with PTMG, an ether polyol, to prepare a water-dispersed urethane resin. The raw materials used are summarized in the table below.

division Raw material name Molecular Weight
(Mw) Cas No. manufacturing company Polyol PDMS Poly(dimethylsiloxane), bis(hydroxyalkyl) terminated 5,600 156327-07-0 Aldrich Poly(dimethylsiloxane), hydroxy terminated 550 70131-67-8 Aldrich PTMG Poly(1,4-butanediol) 2,000 25190-06-1 Aldrich Isocyanate IPDI Isophorone diisocyanate 222.3 4098-71-9 Aldrich Ion addition
/neutralization DMPA 2,2-Bis(hydroxymethyl)propionic acid 134.1 2767-03-7 Aldrich TEAs Triethylamine 101.2 121-44-8 Samchun Chain extender EDAs Ethylenediamine 60.1 107-15-3 Kanto

② Synthesis method

The method of synthesizing water-dispersed PU for surface treatment is to first install a thermometer, stirrer, and reflux condenser in a three-neck reactor, add polyol PDMS and PTMG, stir at room temperature, and remove moisture by vacuum depressurizing at 80°C. . Afterwards, ion addition, reaction with isocyanate, neutralization, and chain extender processes were performed to synthesize a resin for a photocatalyst binder.

③ Experiment results

Siloxane-based polyol and ether-based polyol were used alone or in combination to produce various water-dispersed polyurethanes as shown below. Siloxane-based polyols had different molecular weights, and ether-based polyols used PTMG with a molecular weight of 2,000 to design various composition ratios. The physical properties of the resulting resins were compared and reviewed by checking their appearance characteristics, solid content, viscosity, and film state.

Mixing ratio and basic characteristics of WPU using siloxane-based polyol and ether-based polyol division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 PTMG #2,000 1.5 1.425 1.425 1.35 1.2 1.1 0.9 0.75 PDMS #5,600 - 0.075 - 0.15 0.3 0.45 0.6 0.75 #550 - - 0.075 - - - - - IPDI 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 DMPA 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 TEAs 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 EDAs 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Exterior opacity
white emulsion opacity
white emulsion opacity
white emulsion opacity
white emulsion opacity
white emulsion opacity
white emulsion translucent
white emulsion translucent
white emulsion dispersibility ○ ○ ○ ○ ○ ○ ○ ○ S.C. (%) 19.9 20.6 21.5 26.1 26.9 23.1 27.9 18.2 Viscosity (cps.)
[S63/60rpm] 848~864 1162~1180 580~595 1210~1243 1380 1210 859 352 Film Transparent film, Nontacky Opaque film, Nontacky Translucent film, nontacky, slippery Opaque film, Nontacky, Soft Opaque film, Nontacky, Soft Opaque film, nontacky, soft Transparent film, Nontacky Opaque film, Nontacky

As a result of manufacturing water-dispersed polyurethane including PDMS, an opaque white emulsion was obtained and the viscosity was relatively high. In particular, when PDMS with a molecular weight of 550 was used, the viscosity showed appropriate results, but separation occurred after film production and the film surface became slippery, making use of the binder difficult. In addition, when high molecular weight PDMS was used, there were no problems with the production and stability of the resin. However, although the film characteristics after production are flexible, it is opaque and the surface is highly glossy, so its application as a binder is expected to be somewhat difficult.

me. Manufacture of water-dispersed polyurethane containing perfluorinated additives

① Reaction raw materials are as shown in Table 4.

Raw material name Molecular weight (Mw) Cas No. manufacturing company PPG Poly(propylene glycol) 2,000 25322-69-4 Aldrich DMPA 2,2-Bis(hydroxymethyl)propionic acid 134.1 2767-03-7 Aldrich IPDI Isophorone diisocyanate 222.3 4098-71-9 Aldrich HEMA 2-Hydroxyethyl methacrylate 130.14 868-77-9 Aldrich TEAs Triethylamine 101.2 121-44-8 Samchun PFA Perfluoroalkyl ethyl acrylate - 66605-70-1 DAPACK SDS Sodium dodecyl sulfate 288.4 151-21-3 Aldrich NP-10 Nonylphenol ethoxylate - 26027-38-3 Dongnam APS Ammonium persulfate 228.2 7727-54-0 Aldrich GMA Glycidyl methacrylate 142.15 106-91-2 Aldrich B.A. Butyl acrylate 128.2 141-32-2 Aldrich

② Synthesis method

To produce water-dispersed polyurethane containing perfluorinated additives, perfluoroacryl additives were first prepared. The manufacturing method is to emulsify SDS and NP-10 used as emulsifiers in water, then dropwise add about 10 to 30% of the acryl monomer and initiator relative to the total monomer weight (wt%) in one step, and then incubate at 75 to 80°C. Allow the first reaction to take approximately 1 to 2 hours. Next, step 2 was carried out by adding the remaining acryl monomer and PFA dropwise at the same time as the initiator. In step 2, the initiator and monomer were added dropwise over 1~2 hours at a temperature of 75~80℃ and then aged for 3~5 hours. Next, to manufacture WPU using the perfluoroacryl additive prepared earlier, polyol is first introduced into a nitrogen-filled reactor and then raised to an appropriate temperature (75-80 ℃). After thoroughly mixing Polyol and DMPA, add Isocyanate dropwise over 30 minutes to 1 hour. After dropwise addition, the mixture was stirred for 90 minutes to prepare NCO-prepolymer. After cooling to 50°C or lower, TEA was added dropwise to the reactor for 10 minutes to carry out neutralization. Next, to proceed with urethane-acrylate copolymerization, the temperature was adjusted to 75-80 °C, and then PFA and initiator were added dropwise to the neutralized NCO-terminated prepolymer. After completion of dropwise addition and maturation for 2 to 4 hours, water was added to prepare WPU containing perfluorinated additives. When the viscosity increased during the reaction, MEK and acetone were added to adjust the viscosity, and in the case of the added acetone, the solvent was removed by reducing the pressure after the reaction was completed.

③ Experiment results

Perfluoroacryl polymer composition ratio and basic properties Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 One
step B.A. 20 20 20 20 20 20 20 20 Surfactants
(SDS;NP-10) 10;0 7;3 5;5 3;7 5:5 5:5 5:5 5:5 Initiator 0.2 0.2 0.2 0.2 0.2 0.3 0.2 0.3 2
step B.A. 80 80 80 80 80 80 80 80 GMA 10 10 10 10 10 10 10 10 PFA 5 5 5 5 5 5 3 7 Initiator 0.8 0.8 0.5 0.5 0.8 0.9 0.8 0.8 NaHSO ₃ 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Appearance Phase separation occurs white liquid white emulsion white emulsion white liquid lump formation white liquid white liquid S.C. (%) - 25.12 25.12 25.07 25.11 - 25.07 24.95 Surface tension (mN/m) - 22.98 28.04 20.02 19.65 - 27.21 19.85

As a result of conducting an acrylic copolymerization reaction to produce perfluoroacryl polymer, it was found that as the amount of initiator used increases, the initial reaction speed increases and the molecular weight of the copolymer decreases, thereby improving emulsion stability and lowering surface tension. However, when more than 1% of the initiator was used, the stability of the polymer decreased due to problems in controlling the reaction rate, or lumps formed in the product due to difficulty in controlling the rate. In addition, as the content of PFA, which affects the surface tension of the polymer, increases, the physical properties of the product tend to increase, and it is judged that 5% of the monomer is most appropriate.

Perfluoroacrylate WPU resin composition and basic properties Example 17 Example 18 Example 19 Example 20 Example 21 Example 22 Example 23 Example 24 One
step PPG 2,000 One One One One One One One One DMPA 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 NMP 3% 3% 3% 3% 3% 3% 3% 3% IPDI 3.1 3.1 3.1 3.1 3.1 3.1 3.1 3.1 2
step HEMA 5% 5% 5% 5% 5% 5% 5% 5% TEAs 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 3
step WP-F-5 0% 3% 5% 8% 10% 12% 15% 20% SDS 3% 3% 3% 3% 3% 3% 3% 3% NMP 3% 3% 3% 3% 3% 3% 3% 3% Initiator(APS) 0.05% 0.05% 0.05% 0.05% 0.05% 0.05% 0.05% 0.05% H ₂ O Solid content 20% Appearance translucent yellow translucent yellow translucent yellow translucent yellow translucent yellow translucent yellow translucent yellow translucent yellow Characteristics Nontacky, good physical properties Non tacky, poor physical properties Stiffness medium-hard medium-hard medium-hard Surface tension (mN/m) 49.54 39.45 24.94 22.66 23.11 22.08 21.95 20.01

As a result of manufacturing WPU resin using perfluorinated alkyl acrylate, it was confirmed that the physical properties of the product tend to increase as the amount of perfluorinated additives that directly affect surface tension increases. It is most appropriate when used at about 5 to 8% compared to polyol. It was found that

Next, the manufacturing of the material of the ionizer housing portion will be described in detail.

go. Inorganic antibacterial agent manufacturing research

In order to remove foreign substances on the surface of the shell and improve grinding efficiency, the raw materials are washed - primary grinding and drying process is carried out, high-temperature firing at over 700 ℃ is performed to achieve high purity, and various equipment is used to grind the raw materials to a certain size. A natural inorganic antibacterial agent was prepared by fine grinding and classification.

① First crushing and pre-treatment process: To improve the recovery rate of the shell and remove surface contaminants, the shell is cleaned using a Niagara beater, and then subjected to the first crushing process using a crusher to a size of 5 mm or less. Drying was performed with hot air below 70°C.

② Firing and micronization: In order to maximize the micronization efficiency and purity of the shell, the shell was calcined at a high temperature of over 700°C for more than 5 hours and micronized using a ball mill and grinder.

me. Research on surface modification of inorganic antibacterial agents

In order to improve the physical properties of plastic materials through methods of incorporating antibacterial agents, surface modification methods (silane surface treatment, CA surface coating), and removal of moisture that causes deterioration of physical properties during processing, the following preliminary research was conducted and the physical properties of the molded product were conducted. We aim to establish optimal processing conditions by comparing and evaluating properties.

In the present invention, for the purpose of improving the water resistance of the inorganic antibacterial agent and its compatibility with the applied material, modification was carried out in two ways as follows.

The inorganic antibacterial agent surface-modified using silane (Example 25) showed better compatibility/dispersibility with polymer resin than the inorganic antibacterial agent surface-modified using fatty acid salts (Examples 26 and 27). , the water resistance of the powder itself showed better results in products coated on the surface with fatty acid salts.

Modified Ionized Calcium reforming method Example 25 Silane coating Ionized calcium: TEOS = 100: 1.5 Example 26 fatty acid coating Ionized calcium: Ca-ST = 100:1.5 Example 27 fatty acid coating Ionized calcium: Ca-ST = 100:3
< Properties of modified ionized calcium >

all. Evaluation of antibacterial performance of modified inorganic antibacterial agents

In order to compare and evaluate the antibacterial performance of the modified inorganic antibacterial agents themselves, inorganic antibacterial agents (Examples 25 and 26) were dissolved in distilled water at appropriate concentrations, the supernatant was collected, and an antibacterial experiment was conducted as follows.

① Antibacterial test method for antibacterial agent (liquid)

- Bacteria preparation: E. coli was cultured in LB-broth for 24 hours.

- Antibacterial agent (modified inorganic antibacterial agent dissolved in distilled water) was added to LB-broth at 1.0~0.01% (w/v) in a 50ml tube, inoculated with bacteria, and cultured with shaking for 24 hours.

- After stopping the culture, the supernatant and precipitate were collected and spread on a plate medium.

- Culture: The inoculated medium was cultured again at 37°C, and the number of bacteria was measured after 24 hours.

② Antibacterial test results of antibacterial agent (liquid)

- Strain used: E.Coli (KCTC 12006)

- Sample: CA-1 (Example 25) supernatant, CA-2 (Example 26) supernatant

- Experiment results: A small number of bacteria were detected at low concentrations of silane-modified CA-1 and fatty acid-coated modified inorganic antibacterial agent (CA-2) solutions (inorganic antibacterial agent usage of 0.2% or less), but the number of bacteria was extremely small compared to bacteria growing for 24 hours. Since it is only , it is judged to be an invalid bacterial count.

Both silane-modified inorganic antibacterial agents and Ca-ST modified inorganic antibacterial agents were confirmed to have sterilizing properties.

division Comparative example Example 28 Example
29 Example
30 Example
31 Example
32 Example 33 Example
34 Example
35 control group 1.0%
coating 0.5%
coating 0.2%
coating 0.1%
coating 1.0%
coating 0.5%
coating 0.2%
coating 0.1%
coating Initial bacterial count
[cfu/ ml] 1*10 ⁶
(Ma) - - - - - - - - Bacterial count after 24 hours of growth
[cfu/ ml] 6.8*10 ⁸ (Mb) 0 0 2.1*10 ³ 2.1*10 ² 0 0 1.4*10 ⁴ 1.3*10 ⁴ multiplication value
[mb/ma] 603>30 - - - - - - - - Decrease rate [%] - 100% 100% 100% 100% 100% 100% 100% 100% Antibacterial solution proliferates for 24 hours supernatant sediment

la. Antibacterial plastic material manufacturing

An antibacterial plastic composition was manufactured through a combination of the modified inorganic antibacterial agent prepared previously and an existing commercially available organic antibacterial agent. By examining the fluidity and characteristics of the base resin, two types of base resins, PP and ABS, were used.

The manufactured inorganic antibacterial agent was mainly used as CA-1, which is easy to manufacture and is believed to have better compatibility with the resin due to the introduction of a polar group. It was produced in the form of pellets through a twin-screw extruder with a die temperature of 200 to 250 ℃. An antibacterial plastic composition was prepared. The composition was molded into individual specimens through injection molding, and compatibility between the base resin and the antibacterial agent was confirmed through external appearance. Changes in physical properties and dispersibility due to the antibacterial agent were evaluated by measuring mechanical strength.

① PP-based antibacterial plastic material

Materials Comparative example 2 Example
36 Example
37 Example
38 Example
39 Example
40 Example
41 Example
42 Example
43 Example
44 base polymer PP H1500 100 100 100 100 100 100 100 100 100 100 antibacterial agent biofiller M/B - 10 20 - - - - - - CA-1 - - - 5 - 0.2 0.2 - - - ZPT - - - - 0.2 - - 0.2 - - AG300 - - - - 0.3 0.3 0.5 - - - AGZ300 - - - - - - - 0.3 0.3 0.5 Hardness D type 71 71 69 71 69 70 68 68 68 69 Density g/cc 0.898 0.924 0.955 0.915 0.915 0.904 0.906 0.903 0.905 0.907 tensile strength kg/mm2 3.725 3.54 3.2 3.51 3.505 3.55 3.6 3.49 3.53 3.66 Flexural strength N/mm2 62.4 56.25 52.85 57.4 57.5 63.75 65.6 57.15 63.65 59.85 Flexural modulus N/mm2 2111 2064 1943 2102 1990 2267 2280 1901 2202 2038 Impact strength J/m 17.5 17 11 20.5 18 22 21 21 19.5 16.5 Injection molding conditions (die temperature/cooling time) 210℃/25sec

As shown in Table 9 and Figure 7, when using an antibacterial agent, the hardness of the product decreases somewhat, confirming that processing has an effect of lowering physical properties. As biopila is used in relatively excessive amounts, its proportion increases accordingly. Tensile strength decreases by about 2-15% when antibacterial agents are applied, but only changes of about 5% occur when small amounts of 1 phr or less are used. Flexural strength is somewhat improved, but flexural modulus does not show a consistent trend. Except when using biopillar, impact strength tends to improve somewhat in antibacterial agent-added systems.

In particular, when the surface-modified antibacterial agent of Example 25 is used, the impact strength is improved by 17 to 25%. It can be seen that the combinations of Examples 40 and 41 have excellent overall mechanical strength.

② ABS-based antibacterial plastic material

Materials Comparative example
3 Example
45 Example
46 Example
47 Example 48 Example
49 Example
50 Example
51 Example
52 Example
53 base polymer ABSXR440 100 100 100 100 100 100 100 100 100 100 antibacterial agent biofiller M/B - 10 20 - - - - - - CA-1 - - - 5 - 0.2 0.2 - - - ZPT - - - - 0.2 - - 0.2 - - AG300 - - - - 0.3 0.3 0.5 - - - AGZ300 - - - - - - - 0.3 0.3 0.5 Hardness D type 80 82 82 83 81 82 81 82 80 82 Density g/cc 1.066 1.1 1.084 1.096 1.076 1.072 1.071 1.073 1.076 1.068 tensile strength kg/mm2 6.165 6.12 5.51 5.695 5.995 5.84 5.78 5.745 6.12 6.45 Flexural strength N/mm2 104.6 101.9 93.45 93.2 106.65 106.7 105.65 107.9 109 109.4 Flexural modulus N/mm2 3193 3643 3770.5 3499.5 3201.5 3287 3273.5 3220 3220.5 3414.5 Impact strength J/m 58 19.5 16.5 21.5 44 49.5 51.5 48.5 51 52 Injection molding conditions (die temperature/cooling time) 230℃/25sec

As shown in Table 10 and Figure 8, it can be seen that the hardness of the product slightly increases when an antibacterial agent is used. Tensile strength generally decreases when antibacterial agents are applied. PP has somewhat improved impact strength. In the case of ABS, impact strength tends to decrease significantly. ABS has the disadvantage of discoloring or deteriorating physical properties when combined with oxygen, ozone, or ultraviolet rays in the air. It is possible that the physical properties deteriorated due to the combination with oxygen during mixing. In particular, it is believed that the inclusion of antibacterial agents reduces the flexibility of ABS, thereby significantly lowering the impact strength, and instead increases the flexural strength and flexural modulus by up to 18%. When a small amount of antibacterial agent is added, the decrease in flexibility is suppressed and the rate of decrease in physical properties appears to be somewhat low.

2. Antibacterial plastic performance evaluation: antibacterial test

The antibacterial evaluation of the composition prepared in the present invention was conducted in a laboratory, then a combination with excellent performance was selected, and the performance was evaluated at an accredited institution. First, we conducted an antibacterial test of the antibacterial plastic developed through a culture medium experiment using Staphylococcus aureus.

go. Antibacterial Test Method

① Transfer microorganisms (Staphylococcus aureus) by rubbing them on the medium.

② Create a control group (1 type) with nothing placed on the culture medium and an experimental group (10 types of PP, 10 types of ABS) with specimens (plastic products) of the same size placed on them and culture them in an incubator at 30°C for 12 days.

③ Photograph the shape of the badge every 24 hours. (At this time, a checkerboard-shaped grid was created on the lid of the Petri dish with sections divided at 1 cm intervals horizontally and vertically, and the number of compartments where bacteria were distributed was measured.)

④ Check the medium after 12 days and measure the area of the area where microorganisms have grown.

me. Antibacterial test results

To compare the antibacterial performance of the control group (1 type) and the experimental group (10 types of PP & 10 types of ABS), the size of the clear zone and the number of bacteria were measured. As a result, For both PP and ABS, the best results are seen when 0.3 to 0.5 phr of AG-300 (antibacterial agent) is used.

1) Antibacterial evaluation results of ABS composition

Comparison of clear zone and bacterial count by ABS composition/culture date control group Comparative example
3 Example
45 Example
47 Example
48 Example
49 Example
50 Example
51 Example
52 Example 53 One
Day
car 0 0 0 0 0 0 0 0 0 0 3
Day
car 0 0 0 0 0 0 0 0 0 0 5
Day
car 52 41.5 62 49.5 43.5 52 46 47 49 54 7
Day
car 0.0cm 0.0cm 0.0cm 0.0cm 0.0cm 0.4cm 0.5cm 0.0cm 0.1cm 0.3cm 55.5 46.5 54 42.5 51.5 37.5 33.5 42 39 54 10
Day
car 0.0cm 0.0cm 0.0cm 0.0cm 0.0cm 0.4cm 0.5cm 0.0cm 0.1cm 0.3cm 53 39.5 47 56.5 56.5 52.5 36 46.5 47.5 51.5 12
Day
car 0.0cm 0.0cm 0.0cm 0.0cm 0.0cm 0.4cm 0.5cm 0.0cm 0.1cm 0.3cm 55 37 45 44 47 59 40.5 38 41 56

2) Antibacterial evaluation results of PP composition

Comparison of clear zone and bacterial count by PPS composition/culture date control group Comparative example
2 Example
36 Example
38 Example
39 Example
40 Example
41 Example 42 Example
43 Example
44 One
Day
car 0 0 0 0 0 0 0 0 0 0 3
Day
car 0 0 0 0 0 0 0 0 0 0 5
Day
car 60.5 50 60.5 52 50.5 40 43 47 43.5 40.5 7
Day
car 0.0cm 0.0cm 0.0cm 0.0cm 0.0cm 0.5cm 0.6cm 0.0cm 0.3cm 0.4cm 57.5 47.5 55.5 44.5 50 34 30.5 42.5 38.5 43 10
Day
car 0.0cm 0.0cm 0.0cm 0.0cm 0.0cm 0.5cm 0.6cm 0.0cm 0.3cm 0.4cm 59 57.5 61 43.5 44.5 42 30 46.5 40.5 40 12
Day
car 0.0cm 0.0cm 0.0cm 0.0cm 0.0cm 0.5cm 0.6cm 0.0cm 0.3cm 0.4cm 56 47 60 45 54 41.5 32.5 52 47.5 48

As such, a person skilled in the art will understand that the technical configuration of the present invention described above can be implemented in other specific forms without changing the technical idea or essential features of the present invention.

Therefore, the embodiments described above should be understood in all respects as illustrative and not restrictive, and the scope of the present invention is indicated by the claims described later rather than the detailed description above, and the meaning and scope of the claims and All changes or modified forms derived from the equivalent concept should be construed as falling within the scope of the present invention.

10: Ionizer electrode part 20: Ionizer module part
30: Ionizer housing part

Claims (5)

A photocatalyst mixed with 1 part by weight of phosphoric acid and 9 parts by weight of titanium phosphoric acid,
A photocatalyst coating composition comprising a binder composition in which a siloxane-based polyol, an ether-based polyol, and a perfluorine-based additive are mixed. According to clause 1,
The perfluorinated additives are,
After reacting butylacrylate, surfactant and initiator,
A photocatalyst coating composition prepared by adding and reacting butylacrylate, glycidyl methacrylate, perfluoroalkyl ethyl acrylate, an initiator, and sodium sulfate. Ionizer electrode unit;
an ionizer module portion in which various components that control the ionizer electrode portion are mounted;
It includes; an ionizer housing portion having a space therein to accommodate the ionizer electrode portion and the ionizer module portion;
An ionizer device using a photocatalyst coating composition, characterized in that the photocatalyst coating composition of claim 1 is applied to the surface of the ionizer module portion. According to clause 3,
The ionizer housing part,
An ionizer device using a photocatalyst coating composition comprising a material coated with oyster shell membrane powder with silane or fatty acid salt. According to clause 3,
The ionizer housing part,
Polypropylene polymer or ABS polymer
An ionizer device using a photocatalyst coating composition, characterized in that it contains a material coated with silane or fatty acid salt on oyster shell powder.