KR100581203B1 - Photoless-catalytic paint which have deodorizing, anti-bacterial, and anti-mold effects - Google Patents

Abstract

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a matte multifunctional paint composition having deodorization, antibacterial and mildew under light and matte, and more particularly, ferrous oxide precursor compound, titanium dioxide, acrylic emulsion and An acrylic emulsion paint composition containing a certain amount of fungicides, which continuously performs stable reactions in the absence of light (ultraviolet light) as well as in the absence of light, effectively disinfecting, disinfecting, disinfecting and disinfecting harmful substances. Therefore, the present invention relates to an acrylic emulsion coating composition having deodorization, antibacterial and mold resistance, which can be applied to all living spaces such as interior and exterior walls of buildings, building materials, interiors of vehicles, and interiors without windows.

Ferrous oxide precursor compound, titanium dioxide, deodorant, antibacterial, fungus, acrylic emulsion paint

Description

Photoless-catalytic paint which have deodorizing, anti-bacterial, and anti-mold effects in light and matt

The present invention relates to an acrylic emulsion coating composition having deodorization, antibacterial and mold resistance under light and matting, and more specifically, ferrous oxide precursor compound, titanium dioxide, acrylic emulsion and antibacterial and mildewing agent are contained at a constant mixing ratio. As an acrylic emulsion paint composition, it is able to continuously perform stable reaction not only in the presence of light (ultraviolet light) but also in the absence of light, so that decomposition of harmful substances, antibacterial, sterilization and mold fungus are efficiently performed. The present invention relates to an acrylic emulsion coating composition having deodorizing, antibacterial and moldy properties applicable to all living spaces such as exterior walls and building materials.

Recently, the importance of In door Air Quality (IAQ) in indoor space, called 'Sick House Syndrome', has emerged as a topic of new environmental issues at home and abroad. The interior space is limited and occupies more than 80% of human life, but there is a limit to the lack of environmental regulation and awareness.

Indoor air is contaminated by various volatile organic compounds (VOCs) produced by building materials and artificial facilities, such as building materials and paints, which are used in the construction of new and old buildings. As the polluted air continues to circulate, its concentration is rapidly increasing.

As an alternative, periodic ventilation is important, but above all, more active methods such as elimination, replacement or improvement of sources are required.

As a general method, researches on photocatalyst compositions having light removal and antimicrobial effects by using light and various products containing such photocatalyst compositions are being conducted more actively than ever before.

The photocatalyst has a reaction mechanism in which light (ultraviolet rays) are irradiated onto the surface of the catalyst to generate hydroxyl groups and perhydroxy groups, and decompose substances adsorbed on the photocatalyst surface by their strong oxidizing power. Same as

Removal of volatile organic compounds and antimicrobial photocatalyst coating composition [Korea Patent Publication No. 2001-100052], photocatalytic coating composition with improved hydrophilicity and strength [Korea Patent Publication No. 2003-85108] and anticatalytic activity photocatalyst composition and insect repellent coating [ Korean Patent Registration No. 3954264].

However, these catalysts have been pointed out that the reaction is performed only under limited conditions in which light, i.e., ultraviolet light, is present, so that the reaction is not formed in a dark room or in the absence of light, and thus the effect of the catalyst cannot be obtained.

With these drawbacks, recently, 'air catalysts', which perform the decomposition and harmful action of harmful substances by the oxidation reaction of oxygen and water contained in the air, with or without light, have been proposed as a new alternative.

Titanium phosphate compound, which is the main component of the air catalyst, is milder than titanium photocatalyst, which is the main component, and has little oxidative degradation performance against solids. Recently, it is a material suitable for removing volatile organic compounds such as formaldehyde emitted from building materials and indoors.

However, since the air catalyst of the titanium phosphate compound is not uniformly applied to the substrate, the durability of the reaction is lowered, so there is an effect on instant deodorization, but there is an effective limit to sterilization, antibacterial, etc. requiring a continuous reaction.

Accordingly, the present inventors have made efforts to improve the limitations of the photocatalyst, such as the constraints on light and the reaction persistence of the air catalyst. As a result, titanium dioxide having a strong oxidation power by light and an oxidizing agent exhibiting an effect in a matt state We have developed a new concept of acrylic emulsion paint composition using oxidation and reduction reaction of ferrous ions. Also, ethyl diamine tetraacetate contained in acrylic emulsion paint is a method for improving the stability of ferrous oxide and obtaining a continuous effect. The role of the chelating agent was formed to form chelated iron, and the chelated iron ions reacted with oxygen in the air, thereby discovering that the active oxygen formed performed toxic substance removal and antibacterial effect.

Accordingly, the present invention provides an acrylic emulsion coating composition containing titanium dioxide having a strong oxidation force by light (ultraviolet) and chelated iron having a constant reactivity regardless of the presence or absence of light (ultraviolet) at a constant mixing ratio. There is a purpose.

The present invention is (1) 30-40% by weight of water (2) 3-20% by weight of ferrous oxide precursor compound, (3) 5-25% by weight of titanium dioxide, (4) 15-30% by weight of acrylic resin, And (5) 0.1 to 5% by weight of an antibacterial and mildew agent and 3-5% by weight of (6) ethyldiamine acetate (EDTA).

The present invention will be described in more detail as follows.

The present invention relates to an acrylic emulsion coating composition containing a catalyst composition that continuously exerts the effect of the catalyst not only in the presence of light such as ultraviolet rays or electromagnetic waves, but also in the dark or in the absence of light.

Conventional acrylic emulsion coating compositions have been used in combination with various additives for the removal of harmful substances, antibacterial, bactericidal action.

As such additives, titanium dioxide is already known as a photocatalyst component, and an air catalyst containing a titanium phosphate compound reacting with water and oxygen in the air has been introduced, but the photocatalyst is literally reacted only by light (ultraviolet). There is a limit to the performance, and air catalysts have been pointed out as a lack of persistence of catalysis.

The acrylic emulsion coating composition of the present invention is a coating composition having a continuous catalyst activity even in the absence of light (ultraviolet) as well as in the absence of light, the electrons and holes generated as a result of the reaction with light oxygen in the air And an acrylic emulsion coating composition comprising a mixture of a precursor compound containing ferrous oxide ions and an acrylic resin, which react with water and titanium dioxide, a photocatalytic material that performs catalytic properties, with or without light.

The ferrous oxide ion reacts with oxygen present in the air to form divalent oxygen and trivalent ozone, and the formed oxygen and ozone form an intermediate superoxide anion (O ^2- ) by an oxidation reaction between them. In addition, the active oxygen as the superoxide anion (O ^2- ) is to decompose harmful components attached to the surface, and to have the effect of removing bacteria and fungi.

In general, active oxygen is known to be a harmful oxygen that is constantly produced in various metabolic processes to attack biological tissues to oxidize and damage cells, but oxygen (O ₂ ), which is generated in a large amount in the bio-defense process to remove pathogens or foreign substances, Free radicals such as hydrogen peroxide (H ₂ O ₂ ) also performs a strong antibacterial, bactericidal action.

In addition, the present invention is a method for maintaining the stability of the ferrous oxide ions to exhibit a continuous catalytic effect, ethyldiaminetetraacetate was added to the acrylic emulsion coating composition, this component serves as a chelating agent 1 Oxidation / reduction reaction is performed in the state of iron chelated iron chelate with iron ions.

In general, bivalent ferric oxide is oxidized to trivalent ions as soon as it reacts with oxygen and loses its active effect, but when it is formed as an chelating compound in ionic state, it becomes stable in ionic state with one negative charge. will be.

Looking in more detail the components contained in the acrylic emulsion coating composition of the present invention.

Ferrous oxide ion precursor compounds that oxidize and react with water, oxygen, or air in the air, with or without light (ultraviolet), are in the form of nitrates, sulfates, phosphates and carbonates containing bivalent iron ions and derivatives thereof Although the compound of may be used, it is preferable to use the sulfate form more preferably considering the reactivity.

In addition, the ferrous oxide ion precursor compound may be used by further adding a compound having a charge opposite to that of the iron charge for the purpose of preventing the formation of ferrous oxide ions and preventing oxidation to ferric ions. Can be.

In the present invention, 10 to 30 parts by weight of magnesium sulfate and 10 to 30 parts by weight of sodium sulfate were added to the ferrous oxide ion precursor compound using a sulfate form, and 10 to 30 parts by weight of zinc oxide was used together for heat and light resistance. It was.

The ferrous oxide ion precursor compound is used in 3 to 20% by weight, when the amount is less than 3% by weight, the efficiency for the purpose of lowering the activity of the catalyst is lowered, and when it exceeds 20% by weight solubility in a solvent at room temperature Problem occurs.

In addition, photocatalyst compounds for improving the efficiency of the reaction in the presence of light are generally used in the art, for example, TiO ₂ (Anatase), TiO ₂ (rutile), ZnO, CdS, ZrO ₂ , Although there are V ₂ O ₅ and WO ₃ and the like, it is more preferable to use TiO ₂ (anatase) which is stable and biologically and chemically inert since there is no photocorrosion in consideration of heavy metals, activities and the like.

The photocatalytic compound is used in 5 to 25% by weight, if the amount is less than 5% by weight, the amount is too weak to decrease the activity of the catalyst, if the amount exceeds 25% by weight because the dependence of light is improved There is a problem that the efficiency is reduced when matting.

On the other hand, the photocatalyst and the matte catalyst component are mixed and used in a known acrylic emulsion coating composition.

 Various additives such as leveling agents, pinhole inhibitors, extender pigments, color pigments, and antioxidants may be added to the acrylic emulsion coating composition according to the purpose, and may be used within the range not departing from the object of the present invention. .

The ethyldiaminetetraacetate component in the composition contained in the acrylic emulsion paint serves as a chelating agent for improving the self stability of the ferrous oxide ion.

The acrylic resin is used 15 to 30% by weight, there is no limit to the amount of use, but if the amount is less than 15% by weight may cause a problem in the role of the binder, if the amount exceeds 30% by weight of the matte catalyst of iron 2 compound Problems may affect the properties.

In addition, antimicrobial and mildew agents, which are generally commercially available components, may be added and used for improved sterilization, antibacterial and fungal resistance of the catalyst composition of the present invention. In general, organic and inorganic fungicides, bendiimidazole, triazole, phenolic, sulfone, imide and derivative compounds thereof may be used, specifically 2-pyridinethiol-oxide-sodium salt, N, N-dimethyl- N-phenylsulphimid, diiododimethyl-p-tolisulfone and derivative compounds thereof can be used alone or in combination.

Such antimicrobial and bactericidal substances have a sufficient effect by the compound itself, but when mixed and used in the catalyst of the present invention, even microorganisms can be decomposed.

For example, Escherichia coli produces a toxin called 'endoxin' after the bacterium dies due to its antibacterial effect, which causes fever and, in the worst case, causes severe illness, but by the action of a catalyst, the toxin It can be completely processed until the removal of.

The antimicrobial and mildewing agents are used in an amount of 0.1 to 5% by weight, and when the amount is less than 0.1% by weight, the effect of addition cannot be expected. Since it has the above effect, it does not need to add excessively.

The acrylic emulsion coating composition according to the present invention is prepared by the following conventional method.

The first step is a premixing step in which a ferrous oxide precursor compound, titanium dioxide, an acrylic resin, and an antibacterial and mildew agent are inserted into the premixing tank and premixed.

The second step is a dispersing step, in which the premixed paint is melt-dispersed at 60 to 130 ° C. using an extruder of an extruder and a kneader (PLK-46, PCM-30, ZSK-25), so that it is not a problem in grinding. Made from thick chips.

The third step is a grinding step, in which the chip is pulverized with a high speed mixer and filtered through a 100-200 mesh cloth to complete the manufacture of the paint.

As described above, the acrylic emulsion coating composition of the present invention performs continuous removal of harmful substances and antibacterial effects with or without light by the action of titanium dioxide and chelated iron, and in the presence of light, the action of titanium dioxide is added. More improved effect.

In addition, the addition of antibacterial and fungal agents for improved antimicrobial and bactericidal properties results in better deodorization, antibacterial and fungal effects due to the decomposition of organic substances.Inner and outer walls of buildings, building materials, interiors of vehicles, interiors without windows, etc. Applicable to human living space.

Hereinafter, the present invention will be described in more detail with reference to the following examples, which are not intended to limit the present invention.

Example 1

After pre-mixing uniformly in the mixer for 4 minutes with the composition shown in Table 1, using a melt kneading machine such as Nider (BUSS) or Extruder (ZSK 25, Werner & Pfleider) at 100 ℃ temperature range Melt mixing.

At this time, the melt mixing process was repeated two or more times.

The mixture was cooled in a chill roller, and then ground using a mill mill or disk pin mill, and then passed through a 200 mesh sieve to obtain a paint.

Classification (% by weight) Example 1 Example 2 Example 3 water 40 40 40 Ferrous oxide precursor Ferrous sulfate 10 7 5 Zinc oxide One Magnesium sulfate One Sodium sulfate One Titanium dioxide 10 10 15 Acrylic resin 30 30 30 Ethyldiaminetetraacetate 5 5 5 Antibacterial and mildew agent ¹⁾ 5 5 5 1): A mixture containing 40% by weight of 2-pyridinethiol-oxide-sodium salt, 40% by weight of N, N-dimethyl-N-phenylsulphimid, and 20% by weight of diiododimethyl p-tolisulfone.                                             

Comparative Example 1

An acrylic paint composition of the product name Megaclean (light control paint) having the effect of removing harmful substances, antibacterial, sterilization and deodorization by containing a catalyst as an additive component was set as Comparative Example 1.

Experimental Example 1

In order to determine the effect on the deodorization of the acrylic coating composition of Example 1 and Comparative Example 1, the deodorization rate was measured by the following method is shown in the following table.

[How to measure]

First, a test tube gas was put in a hard vinyl chloride container (600 ml), and the sample prepared by coating the acrylic emulsion coating composition prepared above and dried at room temperature was subjected to a deodorization test. At this time, the initial concentration of the test tube gases such as ammonia, hydrogen sulfide, trimethylamine, methyl mercaptan, and formalin was used at 100ppm. It was.

At this time, the deodorization rate was measured in both light (ultraviolet) irradiation and matt state.

Deodorization rate (%) = (Cb-Cs) / Cb × 100

Cb: blank concentration, Cs: sample concentration

For the deodorant test of the prepared deodorant paint was measured the initial concentration after injecting the test tube gas into a 600ml container. After that, the test paint was added and the concentration change with time was measured.

Deodorization test gas was used ammonia, hydrogen sulfide, trimethylamine, methyl mercaptan, formaldehyde and used an initial concentration of 100ppm.

division Initial concentration (100 ppm) time condition Deodorization rate of compound (%) 3 mins 10 minutes 20 minutes 30 minutes Example 1 Matte ammonia 54 62.3 74 77.5 Hydrogen sulfide 60.2 70.4 75.5 77 Trimethylamine Methyl mercaptan formalin 35 45.8 60.5 62.5 ore ammonia 92 > 98 > 98 > 98 Hydrogen sulfide 92.5 > 98 > 98 > 98 Trimethylamine 93.8 > 98.5 > 98.5 > 98.5 Methyl mercaptan 67 81 90 96.7 formalin 95 > 98.5 > 98.5 > 98.5 Comparative Example 1 Matte Ammonia (500 ppm) no data Hydrogen sulfide no data Trimethylamine no data Methyl mercaptan no data formalin no data ore ammonia no data no data no data 71% Hydrogen sulfide no data Trimethylamine no data Methyl mercaptan no data formalin no data

As shown in the table, it was found that the composition according to the present invention has an excellent deodorization rate against harmful substances such as formaldehyde, ammonia and methyl mercaptan in the presence of light as well as in the absence of light.

Of course, comparing the difference between the deodorization rate in the presence of light and in the absence of light it can be seen that the titanium dioxide is higher in the presence of light to perform the reaction.

Experimental Example 2

In order to determine the antifungal effect of the acrylic emulsion coating composition of Example 1 and Comparative Example 1 was measured by the following method is shown in the following table.

[How to measure]

Test mold strain (mixed strain): Aspergillus niger ATCC 9642

                           Penicillium pinophilum ATCC 11797

                           Chaetomium globosum ATCC 6205

                            Gliosiadium virens ATCC 9645

                            Aureobasidium pullulans ATCC 15233

An acrylic emulsion paint was applied to a 10 cm x 10 m tile, followed by drying for 4 weeks in accordance with ASTM G-21 test method.

Test bacteria Test period 1 week 2 weeks 3 weeks 4 Weeks Example 1 Fungal strains (mixed strains) 0 0 0 0 Comparative Example 1 Fungal strains (mixed strains) 0     0       0      0

As described above, the acrylic emulsion paint composition containing the light and matte components of the present invention is a function of titanium dioxide and chelated iron to remove the harmful substances and the antibacterial activity not only in the presence of light but also in the matt and dark rooms without light. It is expected to be highly applicable because it can be applied to all human living spaces such as interior and exterior walls of buildings, building materials, interior of vehicles, and interiors without windows.

Claims (4)

(1) 30 -40 weight % of water , (2) 3 to 20% by weight of any one ferrous oxide precursor compound selected from nitrates, sulfates, phosphates and carbonates containing divalent iron ions , (3) 5 to 25 wt% of titanium dioxide, (4) 15 to 30% by weight of acrylic resin, (5) Antibacterial and mildew which is one or two or more selected from 2-pyridinethiol-oxide-sodium salt, N, N-dimethyl-N-phenisulfide, diiodimethyldimethyl-p-olisulfone and derivative compounds thereof 0.1 to 5 wt% , (6) ethyldiaminetetraacetate (EDTA) 3-5 weight % A matte acrylic emulsion paint composition, characterized in that it contains. According to claim 1, wherein the ferrous oxide precursor compound is characterized in that the ferric sulfate alone or ferrous sulfate further contains one or two or more selected from zinc oxide, magnesium sulfate and sodium sulfate. Matte acrylic emulsion paint composition. delete delete