KR102160277B1 - Coating composition that slowly releases chlorine dioxide for adsorption and decomposition of formaldehyde emitted from artificial wood plates - Google Patents

Abstract

The present invention relates to a composition for adsorbing, decomposing, and shielding formaldehyde released from adhesives, artificial plates such as plywood, a particle board, and medium-density fiberboard, and the like. The present invention relates to a lamination coating solution composition for slowly releasing chlorine dioxide, which activates chlorine dioxide by adding a reaction delay activator capable of releasing chlorine dioxide slowly and continuously, wherein the composition comprises a first composition and a secondary composition. Chlorine dioxide, which decomposes aldehydes into safe substances such as carboxylic acid or formic acid upon reaction, is released slowly and continuously for a long time so as to maintain reactivity with formaldehyde, and constitutes a heterogeneous adsorbent with optimal pores for adsorbing formaldehyde, and the heterogeneous adsorbent is pre-supported in a water-soluble polymer solution in which chlorite, a precursor of chlorine dioxide, is dissolved, and a polymer resin adhesive having shielding properties is added to the supported heterogeneous adsorbent to constitute the first composition. The secondary composition is formed by adding additives such as a dispersing agent, a thickening agent, an antifoaming agent, and a fluidizing agent that can adjust working properties according to the use of the composition. The composition can purify indoor air by adsorbing, decomposing, and shielding formaldehyde, which is a harmful substance generated from artificial plates.

Description

Coating composition that slowly releases chlorine dioxide for adsorption and decomposition of formaldehyde emitted from artificial wood plates}

The present invention relates to a laminated coating liquid composition comprising a heterogeneous adsorbent for adsorbing formaldehyde released from an artificial plate and a heterogeneous adsorbent for sustained release of chlorine dioxide decomposing adsorbed formaldehyde. .

This composition consists of formaldehyde (molecular size 2.1 Å) and benzene, a volatile organic compound. Disperse a heterogeneous adsorbent with optimal pores capable of adsorbing harmful substances such as toluene (molecular size 6.8~8Å) in a water-soluble polymer aqueous solution in which chlorite is dissolved to support chlorite, and then support heterogeneous After forming the primary composition by adding a polymeric resin adhesive having shielding properties to the aqueous adsorbent of the composition, additives such as dispersants, thickeners, defoaming agents, and fluidizing agents are added to make a secondary composition so that the work properties can be adjusted according to the use of the composition. , As a laminated coating liquid composition that activates chlorine dioxide by adding a reaction delay activator that can sustainably release chlorine dioxide, it absorbs, decomposes, and shields formaldehyde, a representative harmful substance generated from artificial plates, for a long and continuous period of time. It relates to a composition for purifying.

In general, volatile organic compounds and harmful substances generated from construction materials, adhesives, wallpaper, paints, etc. used in new buildings or new furniture cause discomfort in the health and indoor life of residents.

Representative hazardous substances among these volatile organic compounds include formaldehyde, benzene, toluene, acetone, and styrene, and these substances are slowly released over a long period of time, causing acute or chronic disease to residents.

As a method for removing organic volatile substances including formaldehyde, a physical method using adsorption, a chemical method for converting volatile substances into other substances, or a combination of both are mainly used.

To remove VOCs by adsorption, activated carbon, zeolite, silica gel, bentonite, loess, and adsorbents such as high adhesive starch are mainly used.

In order to cause chemical changes with such adsorbents, a photocatalyst containing a titanium dioxide solution as the main material is used (registered patent publication No. 10-1328657) or a removal method using a platinum catalyst (registered patent publication No. 10-1319064), aluminum and calcium A method of pulverizing a contained material, replacing it with zinc, copper, iron, and silver ions, and adding a material obtained by reaction with an ammonia material to an adsorbent (Patent Publication No. 10-2009-0116846) has been reported. However, this method requires a light source such as ultraviolet rays to remove substances such as formaldehyde, and its role is limited in the form of a dark room, and its manufacturing method is a complex process, i.e., high temperature reaction temperature, filtration, drying, pulverization, etc. It has the disadvantage of being manufactured through.

In addition, as a substance used for chemical removal of formaldehyde, a substance obtained by reacting organic acids and ammonia at 100-150°C (Public Patent Publication No. 10-2009-0120066) or hydrogen peroxide by decomposition of sodium percarbonate There is a method of removing formaldehyde by releasing the formaldehyde (Registration Patent Publication No. 10-0480808), but these methods also require high temperatures in the manufacturing process, and the process of releasing hydrogen peroxide is sensitive to temperature and humidity. The removal efficiency of the product is improved.

In particular, it absorbs and removes harmful substances and volatile organic compounds generated from adhesives of artificial boards such as plywood, particle board, and medium-density fiber board, which are interior finishing materials used as main materials for interior materials of buildings, kitchens, warehouses, dishwashers, automobiles, and furniture. Various adsorption compositions that can be used have been published (Patent Publication No. 10-2015-0114217), which is made by adding electrolytic reduced water adsorbed to pyrite, graphite, bentonite, etc., sodium chloride, a deliquescent substance, and hydrogen peroxide that causes an oxidation reaction under acid conditions. Adsorption compositions are published, but this is an adsorption composition using the adsorption power of mordenite, activated carbon, and bentonite. While the particle diameter of the adsorbent is small, there is no mention of the adhesion between the pores of the adsorbent and the target, which are related to efficiency. It has a significant difference from the present invention.

Korean Patent Publication No. 10-1328657 Korean Patent Publication No. 10-1319064 Korean Patent Application Publication No. 10-2009-0116846 Korean Patent Application Publication No. 10-2009-0120066 Korean Patent Publication No. 10-0480808 Korean Patent Application Publication No. 10-2015 -0114217

The present invention is a safe material such as carboxylic acid or formic acid by reacting with aldehydes and an adsorbent composition optimized for adsorbing formaldehyde particles in order to adsorb, decompose, and shield formaldehyde emitted from artificial plates such as plywood, particle board, and medium-density fiberboard. It is to provide a laminated coating composition using the reactivity of chlorine dioxide to be converted.

However, since chlorine dioxide is an unstable substance that boils at 1 degree and volatilizes, in order to stably release it, an adsorbent capable of adsorbing formaldehyde particles and a heterogeneous adsorbent with large pores are composed of a water-soluble polymer solution in which chlorite is dissolved. Provides a laminated coating composition composed of an adhesive that is dispersed and supported in advance and has a shielding power in an aqueous solution of chlorite-soluble polymers supported with different types of adsorbents, a reaction delay activator that generates chlorine dioxide, and an additive that changes the physical properties of the composition for each purpose. Therefore, it is intended to purify indoor air quality by adsorbing, decomposing, and shielding formaldehyde, which is a harmful substance of artificial plates.

As a means to achieve such a technical problem, several kinds of adsorbents with optimal pores for adsorbing formaldehyde particles are constructed,

1) preparing a first adsorbent (a) made of aluminum silicate having a void of 4 to 8 angstroms capable of adsorbing formaldehyde, and

2) Diatomaceous earth and talc with pores of 5 to 100 nm. Preparing a second adsorbent ⒝ and a dispersant made of illite, and

3) After the first adsorbent (a) made of aluminum silicate is supported in a water-soluble polymer aqueous solution, chlorite is infiltrated into the pores of aluminum silicate, and then the second adsorbent (⒝) is sequentially mixed, and a polymer resin adhesive of glycidyl acrylic resin is added. Added to constitute the primary composition (A), or,

4) A secondary composition (B) is formed by adding an additive consisting of a thickener, an antifoaming agent, and a fluidizing agent that can adjust the work properties according to the use of the primary composition (A)

5) Separately, 100 g of a water-soluble polymer aqueous solution in which 1.25 g of chlorite, a precursor of chlorine dioxide, is dissolved is mixed with the prepared primary composition (A) or secondary composition (B) to activate chlorine dioxide. It is characterized in that it formed.

The present invention configured as described above provides beneficial effects to the human body by adsorbing, decomposing, and shielding formaldehyde, which is a representative harmful substance generated from building materials, adhesives, wallpaper, paint, etc. used in new buildings or new furniture to purify indoor air quality. I made it possible to do it.

The present invention relates to a composition for adsorbing, decomposing, and shielding formaldehyde released from artificial plate adhesives such as plywood, particle board, and medium-density fiber board, and the composition is a medium. Synthetic boards exposed with a liquid composition that adsorbs, decomposes, and shields formaldehyde continuously released from furniture, desk drawers, wardrobes, windows, shelves, cupboards, sinks, etc. that are exposed to invisible places inside low-cost construction materials without finishing. It can be used by spraying or applying it on.

The present invention is an optimal adsorbing material for adsorbing formaldehyde in order to utilize the reactivity of chlorine dioxide, which decomposes into safe substances such as carboxylic acid or formic acid when reacting with aldehydes and the composition of an adsorbent optimized for the adsorption of formaldehyde particles, which are harmful substances. A different type of adsorbent with pores is formed, and a different type of adsorbent is pre-loaded in a water-soluble polymer solution in which chlorite, a precursor of chlorine dioxide, is dissolved, and a polymer resin adhesive having shielding properties is added to the supported dissimilar adsorbent. After the primary composition is prepared, a secondary composition is formed by adding additives such as a dispersant, a thickener, an antifoaming agent, and a fluidizing agent to adjust the working properties according to the use, and then a reaction delay activator capable of sustained release of chlorine dioxide is used. It is a laminated coating liquid composition that activates chlorine dioxide in heterogeneous adsorbents supported by adding it.It adsorbs, decomposes, and shields formaldehyde, a harmful substance generated from artificial plates, thereby purifying the indoor air quality and giving beneficial effects to the human body.

1 is a schematic cross-sectional view of a schematic ring for continuously reacting and decomposing and removing formaldehyde while chlorine dioxide supported on a heterogeneous adsorbent is slowly released.

Hereinafter, an embodiment of the present invention will be described in detail.

The present invention is composed of an adsorbent optimized for adsorption of formaldehyde particles to adsorb, decompose, and shield formaldehyde emitted from artificial boards such as plywood, particle board, and medium-density fiber board, and react with aldehydes to react with carboxylic acid or formic acid. It relates to a laminated coating composition using the reactivity of chlorine dioxide to convert it into a safe material such as.

Looking at the method for preparing a lamination coating composition using the reactivity of chlorine dioxide of the present invention,

1) Prepare a first adsorbent (a) made of aluminum silicate with a pore of 4 to 8 angstroms capable of adsorbing formaldehyde.

2) Diatomaceous earth and talc with pores of 5 to 100 nm. Prepare a second adsorbent (⒝) made of illite and a dispersant.

3) After the first adsorbent (a) made of aluminum silicate is supported in a water-soluble polymer aqueous solution, chlorite is permeated into the pores of the aluminum silicate, and then the second adsorbent (⒝) is sequentially mixed, and a polymer resin adhesive of glycidyl acrylic resin is added. It is added to prepare and prepare the primary composition (A).

4) A secondary composition (B) is prepared and prepared by adding an additive consisting of a thickener, an antifoaming agent, and a fluidizing agent capable of adjusting the work properties according to the use of the primary composition (A).

5) After preparing the first composition (A) or the second composition (B), 100 g of a water-soluble polymer aqueous solution in which 1.25 g of chlorite, which is a chlorine dioxide precursor, is dissolved separately is added to the prepared first composition (A) or second composition. (B) is mixed to form a chlorine dioxide sustained-release laminated coating liquid composition that activates chlorine dioxide.

A specific manufacturing process for preparing the chlorine dioxide sustained-release laminated coating composition for activating chlorine dioxide prepared as described above is as follows.

First, a precursor to separately generate chlorine dioxide is selected from sodium chlorite, calcium chlorite, and lithium chlorite, and water-soluble polymer materials that will act as a reaction delay and buffer are agar, hydroxypropylmethylcellulose, starch, One or more types of carginane are selected and 1.25 g of chlorite is dissolved in a 1.5% aqueous solution to prepare 100 g of a dissolved aqueous polymer solution.

The prepared water-soluble polymer aqueous solution is dissolved in a concentration of 0.5 to 5% chlorite for 3 hours or more to prepare a water-soluble polymer aqueous solution.

In addition, the first adsorbent of different types consisting of aluminum silicate with 4 to 8 angstrom pores capable of adsorbing formaldehyde⒜ is selected from bentonite, silica gel, moderite, zeolite, sepiolite, and aluminum silicate. do.

The average particle diameter of the selected first adsorbent ⒜ must be 4 microns or less, and the particles form micropores of 8Å (angstrom) or less.

One type of first adsorbent (⒜ 3 to 10 parts by weight) selected relative to 100 parts by weight of the prepared water-soluble polymer aqueous solution,

Compared to 100 parts by weight of the water-soluble polymer aqueous solution, an adsorbent made of any one of morderite, bentonite, sepiolite, diatomaceous earth, and ocher, and another amorphous second adsorbent having a large pore of 5 to 100 nm (5 to 20 parts by weight consisting of ⒝,

A third adsorbent ⒞ consisting of 10 to 20 parts by weight selected from heavy calcium carbonate, talc, chlorite, hard calcium carbonate, titanium oxide, illite, etc. is prepared for the fluid physical properties of the constituent materials relative to 100 parts by weight of the aqueous polymer solution.

The first, second, and third adsorbents of different types are sequentially mixed with a water-soluble polymer aqueous solution in which one type of chlorite is selected and dissolved, and stirred at room temperature at 1000 rpm or less for 1 hour or more to form a first composition.

In the first composition, one or more adhesives selected from polymer resin composites such as styrene-butadiene/nitrile-butadiene latex, polyvinyl alcohol, polyvinyl acetate, ethyl vinyl acetate, urethane resin, acrylic resin, etc. Mixing 3-10 parts by weight based on parts by weight, and 0.5 to 1% of a defoamer selected from mineral-based and silicone-based alcohol-based for the properties of the laminated coating, and a polyacrylic acid-based or phosphate-based dispersant based on 100 parts by weight of the primary composition (A) After selecting and adding 0.5 to 2% by weight, the mixture is stirred at 500 rpm or less for 60 minutes or longer to complete the secondary composition (B).

In addition, citric acid is an activator that will activate the dissimilar first, second, and third adsorbents, which are dissolved in a water-soluble polymer material and supported with chlorite. An organic acid such as acetic acid and maleic acid, or an inorganic acid such as hydrochloric acid, sulfuric acid, sodium hydrogen sulfate, etc., is selected and mixed with the secondary composition (B) and stirred at 500 ppm or less for 1 hour or more to form a laminate coating composition.

In more detail, different types of adsorbents are selected from bentonite, silica gel, morderite, zeolite, sepiolite, aluminum silicate, etc., and the average particle diameter must be 4 microns or less, and the particles must be 8Å (angstroms) or less. A type of first adsorbent⒜ having a ⒜, and a type of amorphous second adsorbent⒝ having a large pore of 5 to 100nm among adsorbents such as moderite, bentonite, sepiolite, diatomaceous earth, and loess, and heavy calcium carbonate and talc for fluid physical properties. Chlorine dioxide that adsorbs and decomposes formaldehyde released from artificial plates by dispersing and supporting a kind of third adsorbent⒞ selected from chlorite, hard calcium carbonate, titanium oxide, illite, etc. in a chlorite-soluble polymer material in order at 1000 rpm for more than 60 minutes It constitutes a sustained-release laminated coating solution composition.

In particular, in the present invention, formaldehyde adsorbed by different types of adsorbents with different pores meets and reacts with chlorine dioxide that is already released slowly in the adsorbent, and formaldehyde continuously generated inside the plate is adsorbed by different types of adsorbents and decomposes chlorine dioxide. It is trapped in the polymer resin adhesive film and cannot be released out of the artificial plate.

Specifically, the present invention adsorbs formaldehyde in order to utilize the reactivity of chlorine dioxide, which is optimized for adsorbing formaldehyde particles, which are harmful substances, and decomposes into safe substances such as carboxylic acid or formic acid when reacting with aldehydes for a long-term and continuous use. A polymer resin having a shielding property on the supported different types of adsorbents by constituting different types of adsorbents with optimal pores, pre-loading them in a water-soluble polymer aqueous solution in which chlorite, a precursor of chlorine dioxide, is dissolved. After preparing the primary composition (A) to which the adhesive is added, the secondary composition (B) is formed by adding additives such as a dispersant, a thickener, an antifoaming agent, and a fluidizing agent to adjust physical properties according to the use, and then release chlorine dioxide slowly. As a laminated coating liquid composition that activates chlorine dioxide by adding a reaction delay activator that can be used, it purifies the quality of indoor air by adsorbing, decomposing, and shielding formaldehyde, a harmful substance generated from artificial plates.

The chlorine dioxide is a powerful oxidizing agent, a compound widely known as bleaching, deodorizing, disinfecting and disinfecting.

The chlorine dioxide oxidizes formaldehyde, ammonia, pyrrole (-SH), sulfide (R-S-R'), phenol, and the like in air to convert it into other substances. In particular, formaldehyde is converted to formic acid by chlorine dioxide and ultimately to carbon dioxide.

Looking at this in detail,

Aldehyde + ClO2 → oxidation to carboxylic acid

Acetaldehyde (CH3CHO) + ClO2 → Formic acid (CH3COOH)

Formaldehyde (HCHO) +ClO2 → formic acid (CH3COOH).

However, even with the excellent effect of chlorine dioxide, its use is limited due to its physical properties, that is, its low boiling point (bp: 11℃).

In order to compensate for the physical properties of chlorine dioxide, the present invention constitutes several kinds of adsorbents having optimal pores for adsorbing formaldehyde particles, and for a composition for sustained release of chlorine dioxide, a water-soluble polymer aqueous solution is prepared, and then chlorite is used. After dissolving, adding several kinds of adsorbents to this in sequence, dispersing and supporting, and then mixing a polymer resin adhesive having a shielding function to the adsorbent supported in an aqueous chlorite solution to form a primary composition (A).

The primary composition (A) is composed of a secondary composition (B) by adding additives such as a dispersing agent, a thickening agent, an antifoaming agent, and a fluidizing agent so that the working properties can be adjusted according to the use.

After the secondary composition (B) is prepared, a reaction delay activator that can sustainably release chlorine dioxide is added, mixed and stirred to form a laminated coating liquid composition, which is a representative harmful substance generated from artificial plates. The composition was decomposed and shielded to continuously purify indoor air quality for a long time.

In addition, the composition for each step is as follows.

The composition is composed of heterogeneous porous adsorbents, chlorite, activators, adhesives, and additives. In the step of preparing heterogeneous adsorbents with optimal pores capable of adsorbing formaldehyde particles (2.1Å) (異) kinds of adsorbents are selected from bentonite, silica gel, morderite, zeolite, sepiolite, aluminum silicate, etc., and the average particle diameter must be 4 microns or less, and the particles have micropores of 8Å (angstrom) or less. (One) 3 to 10% of the adsorbent is used, preferably aluminum silicate is good for adsorbing formaldehyde. If the particle diameter is larger than 4 microns, roughness may appear when sprayed or applied, and if it is smaller, compatibility with different types of adsorbents is poor. Contrary to the particle size, the particle pore size is less than 8 angstroms for adsorption of formaldehyde (2.1Å) and benzene/toluene (6.8~8Å).

In addition, with respect to 100 parts by weight of the water-soluble polymer aqueous solution, 5 to 20 parts by weight consisting of an adsorbent made of any one of morderite, bentonite, sepiolite, diatomaceous earth, and ocher of 5 to 20 parts by weight of an irregular first adsorbent ⒜ having a large pore of 5 to 100 nm, and, For the fluid physical properties of the constituent materials, a third adsorbent composed of 10 to 20 parts by weight selected from heavy calcium carbonate, talc, chlorite, hard calcium carbonate, titanium oxide, and illite (compared to 100 parts by weight of the aqueous polymer solution) is prepared. .

As a precursor to generate chlorine dioxide, select a kind of chlorite, such as sodium chlorite, calcium chlorite, and lithium chlorite, and as a water-soluble polymer material that will act as a reaction delay and buffer, CMC (carboxymethyl cellulose), agar , Hydroxypropylmethylcellulose, starch, carginane, and dissolving at a concentration of 0.5 to 5% for at least 3 hours to form a water-soluble polymer aqueous solution, and then selecting and dissolving one of the prepared chlorite salts. , After mixing different types of adsorbents and stirring at room temperature for 1 hour or more at 1000 rpm or less to form the first composition (A), a polymer resin composite styrene-butadiene/nitrile-butadiene latex based on 100 parts by weight of the first composition , Polyvinyl alcohol, polyvinyl acetate, ethyl vinyl acetate, urethane resin, acrylic resin, etc., 3-10 parts by weight of one or more adhesives are mixed, and 0.5~ selected from mineral-based and silicone-based alcohol-based antifoaming agents for the properties of the laminated coating. 1 part by weight and 0.5 to 2 parts by weight of polyacrylic acid-based or phosphate-based dispersant are added and stirred at 500 rpm or less for 60 minutes or more to complete the secondary composition (B).

In addition, citric acid is used as an activator for chlorine dioxide in a heterogeneous adsorbent that is dissolved in a water-soluble polymer material and supported by chlorite. Select one of organic acids such as acetic acid and maleic acid or inorganic acids such as hydrochloric acid, sulfuric acid, and sodium hydrogen sulfate, dissolve in the aqueous polymer solution above, and mix 0.5 to 2 parts by weight based on 100 parts by weight of the secondary composition for 1 hour at 500 ppm or less Stir over to constitute a composition.

In addition, the sustained-release chlorine dioxide laminated coating composition may be sprayed or applied to an artificial plate, and may be applied alone or mixed with an adsorbent to adsorb and decompose formaldehyde generated from the exposed artificial plate.

In addition to the concentration and viscosity of the chlorite and organic acids used in this composition, the sustained release of chlorine dioxide is greatly affected by the particle size and pores of the adsorbent supported in the aqueous polymer solution in which chlorite is dissolved. Chlorine dioxide can be released slowly up to 0.7mg/day-3mg/day (Table 1, Table 2).

The formaldehyde removal ability of the sustained-release chlorine dioxide layered coating composition thus prepared is confirmed by Examples 1 and 2 and Comparative Examples 1. 2.

In addition, the chlorine dioxide generating composition may be sealed with a packaging material such as PA/LDPE, PET/LDPE, or Multi-LDPE to be used as a sustained-release chlorine dioxide laminated coating composition pack.

In Examples 1 and 2, the ability of the layered coating composition to remove formaldehyde by the sustained-release layered coating composition is remarkable in the ability of the layered coating composition to slowly release chlorine dioxide according to the particle diameter and pores of the adsorbent at the same concentration and viscosity. It shows a difference, and the higher the amount of chlorine dioxide released from the coating composition, the higher the ability to remove formaldehyde. The results show that formaldehyde is easily oxidized by chlorine dioxide in the laminated coating.

In addition, formaldehyde removal efficiency can greatly increase formaldehyde removal efficiency by mixing porous crystalline alumina silicate having pores suitable for adsorption of formaldehyde in addition to the amount of chlorine dioxide generated.

The adsorbent used in the present invention is a synthesized porous crystalline alumino silicate capable of specifying and adsorbing formaldehyde.

The adsorbent is a colloidal silicate aqueous solution and an organic cellulose compound to prepare a molded article, and then calcined to remove the cellulose-based compound, and then treated with an aqueous alkali metal solution and an aqueous sodium aluminate solution to determine the inorganic binder component silica, which is porous. It is characterized in that it consists of a powder or a spherical molded body directly converted to alumino silicate.

The alumina silicate adsorbent is a powder adsorbent of less than 4 microns with 4Å~8Å pore size, volume, and the adsorption capacity of formaldehyde is superior to that of other kinds of natural adsorbents, and the particle pores are an important factor in removing formaldehyde. It appears well in Examples 3 to 5 and Comparative Examples 2 to 3.

In Examples 1 to 5, the pore diameter of the aluminum silicate is 4Å to 8Å, the formaldehyde removal effect was exhibited, more preferably the aluminum silicate having a pore diameter of 5Å.

In addition, in Examples 3 to 5, in the case of alumina silicate having an adsorbent pore diameter of 5Å and 8Å, the reduction in formaldehyde after 4 hours was 94.5% and 92.3%, respectively, about 3% and 0.8 than that of alumina silicate with a diameter of 4.2Å. % Increased. This suggests that the pore size of alumina silicate is an important factor in the adsorption of formaldehyde.

It has been experimentally confirmed that alumina silicate having specific pores acting as an adsorbent for sustained-release layered coating composition of chlorine dioxide is effective in adsorbing formaldehyde even when used alone, but the use of alumina silicate alone has the function of adsorbing and removing formaldehyde. At the same time, it has the disadvantage that it is possible to escape.

This problem can be removed by reacting with adsorbed formaldehyde and free formaldehyde by slow release of chlorine dioxide from the adsorbent on which chlorine dioxide is supported.

That is, even if the adsorption and release of formaldehyde from the alumina silicate and heterogeneous adsorbents present inside the laminated coating composition are repeated, formaldehyde is oxidized by chlorine dioxide continuously generated in the composition and converted to formic acid, and the produced acid is alkali or alkali. It becomes salt by earth metal base, and its volatility disappears, increasing the effect of removing formaldehyde.

Hereinafter, preferred embodiments are presented to aid in understanding the present invention. However, the following examples are provided for easier understanding of the present invention, and the contents of the present invention are not limited by the following examples.

< Measurement of sustained release of chlorine dioxide of coating composition >

To measure the adsorption and control rate of formaldehyde, select different types of adsorbents, prepare a coating composition while changing the pore diameter of the adsorbent, coat 30g on a 10cm×20cm glass plate, and then formaldehyde in a simple Tedler bag (100 parts by weight of the coating composition). About 35 parts by weight of formaldehyde solution, extra grade) 0.12ml (2ppm) was put into a syringe and inhaled with a Professional Air Tester (No, WP6900) every hour to measure the change in the formaldehyde concentration inside the simple Tedler bag. The measurement of the daily release of chlorine dioxide generated from the coating composition is based on the Annex 17 Method of Analysis of Chlorine Dioxide and Chlorite ions in the Korea Waterworks and Sewerage Association (KWWA)'s Evaluation Test Method It was measured by putting it in a nonwoven fabric maintaining liquid airtightness that allows permeation of chlorine dioxide.

< Example 1>

The average particle diameter of the adsorbent is 4 microns or less, and the first adsorbent of aluminum silicate with micropores of 8Å (angstrom) or less⒜ 5 parts by weight and diatomaceous earth 6 parts by weight of 5 to 100 nm pores, talc 3 parts by weight, illite furnace After preparing 5 parts by weight of the second adsorbent ⒝ consisting of 5 parts by weight of the mixture, 1.25 g of sodium chlorite is dissolved in 1.5 parts by weight of CMC (carboxymethyl cellulose) aqueous solution, 0.6 parts by weight of dispersant is added, and then the above three adsorbents are added in order. The mixture is mixed and stirred at room temperature at 1000 rpm or less for 1 hour or more to form the first composition (A).

The mixing ratio of the first and second adsorbents and the dispersant is composed of parts by weight of each adsorbent based on 100 parts by weight of the aqueous polymer solution.

4 parts by weight of a glycidyl-based acrylic resin was mixed with respect to 100 parts by weight of the primary composition (A), and 0.4 parts by weight of an alcohol-based antifoaming agent was added, followed by stirring at 500 rpm or less for 60 minutes or longer to prepare a secondary composition (B). Complete.

In addition, 2.2 g of citric acid was dissolved in an aqueous solution of 1.5 parts by weight of CMC based on 100 parts by weight of a water-soluble polymer aqueous solution, mixed with the secondary composition, and then stirred at 500 ppm or less for 1 hour to prepare a laminate coating composition.

The composition was sealed with a liquid-tight film capable of permeating chlorine dioxide, and the daily release amount of chlorine dioxide was measured at 25°C (see Table 1).

Table 1 shows the daily chlorine dioxide emission.

<Example 2>

Under the same conditions as in Example 1, a layered coating composition was prepared by changing the input amount to 2.00 g of sodium chlorite and 3.50 g of citric acid, and the composition was sealed with a liquid-tight film capable of permeating chlorine dioxide to reduce the daily amount of chlorine dioxide released. It was measured at °C (see Table 2).

Table 2 shows the daily chlorine dioxide emission.

<Example of formaldehyde removal implementation>

The average particle diameter of the first adsorbent ⒜ is 4 microns, and the first adsorbent ⒜ of aluminum silicate having pores of 8Å (angstrom) or less is 5 parts by weight per 100 parts by weight of water-soluble polymer aqueous solution, and diatomaceous earth with pores of 5 to 100 nm. 6 parts by weight, 3 parts by weight of talc. After preparing a second adsorbent ⒝ consisting of 5 parts by weight of illite, 0.6 parts by weight of a dispersant was added to a solution in which 1.25 g of sodium chlorite was dissolved in 1.5 parts by weight of CMC based on 100 parts by weight of the water-soluble polymer aqueous solution. 2 After mixing the adsorbent in order and stirring at room temperature at 1000 rpm or less for 1 hour or more to form the first composition (A), 4 parts by weight of a glycidyl-based acrylic resin adhesive was mixed with respect to 100 parts by weight of the first composition, and alcohol-based After adding 0.4 parts by weight of antifoaming agent, stirring at 500 rpm or less for 60 minutes or more to complete the second composition, and then dissolving 2.2 g of citric acid in 1.5 parts by weight of CMC based on 100 parts by weight of the aqueous polymer solution, and then mixing it with the second composition (B). Then, the mixture was stirred at 500 ppm or less for 1 hour to prepare a laminated coating composition.After coating 30g on a 10cm×20cm glass plate, formaldehyde in a simple Tedler bag (35 parts by weight of formaldehyde solution, extra Grade) 0.12ml (2ppm) was put into a syringe and inhaled with a Professional Air Tester (No, WP6900) every hour to measure the change in the concentration of organic volatile substances and formaldehyde inside the simple Tedlar bag.

< Example 1>

The laminated coating composition of Example 1 was prepared and the change in formaldehyde was measured.

< Example 2>

The laminated coating composition of Example 2 was prepared and the change in formaldehyde was measured (see Table 3).

Table 3 shows the amount of change in formaldehyde over time of the composition.

< Comparative example 1>

Prepare a combination excluding sodium chlorite and citric acid, which are involved in the mechanism of chlorine dioxide generation.

In the same formulation as above, the average particle diameter of the first adsorbent is 4 microns or less, 5 parts by weight of the first adsorbent of aluminum silicate having pores of 8 Å (angstroms) or less, 6 parts by weight of diatomaceous earth with pores of 5 to 100 nm, talc 3 Parts by weight. After preparing the second adsorbent prepared with 5 parts by weight of illite, 0.6 parts by weight of dispersant was added to the aqueous solution of 1.5 parts by weight of CMC based on 100 parts by weight of the water-soluble polymer aqueous solution, and then each of the adsorbents was sequentially mixed for 1 hour at room temperature at 1000 rpm or less The first composition was formed by stirring the above. (The first and second adsorbents represent parts by weight based on 100 parts by weight of the aqueous polymer solution).

4 parts by weight of a glycidyl-based acrylic resin adhesive was mixed with respect to 100 parts by weight of the prepared primary composition, 0.4 parts by weight of an alcohol-based antifoaming agent was added, and then stirred at 500 rpm or less for 60 minutes or more to prepare a laminated coating composition. After coating 30g on a 20cm glass plate, add 0.12ml (2ppm) of formaldehyde (35 parts by weight of formaldehyde solution, extra level) to 100 parts by weight of the laminated coating composition into a simple Tedler bag with a syringe and a Professional Air Tester ( No, WP6900) and measured the change in the concentration of organic volatile substances and formaldehyde inside the simple Tedlar bag.

< Example 3 to 5 and Comparative example 2>

In Examples 3 to 5, the average particle diameter of the first adsorbent ⒜ is 4 microns, and 5 parts by weight of aluminum silicate having pores of 4.2 to 8Å (angstroms) or less (Comparative Example 2 is 5% natural zeolite parsed stone) and 5 to 100 nm After preparing 6 parts by weight of diatomaceous earth, 3 parts by weight of talc, and 5 parts by weight of illite of the pores of, 1.25 g of sodium chlorite was dissolved in an aqueous solution of 1.5 parts by weight of CMC based on 100 parts by weight of the aqueous polymer solution, and 0.6% of dispersant was added. After (parts by weight based on 100 parts by weight of the aqueous polymer solution), the first and second adsorbents were sequentially mixed and stirred at room temperature at 1000 rpm or less for 1 hour or more to form the first composition (A), and then the first composition 100 4 parts by weight of a glycidyl-based acrylic resin adhesive was mixed with the first composition (A) based on parts by weight, 0.4 parts by weight of an alcohol-based antifoaming agent was added, and then stirred at 500 rpm or less for 60 minutes or more to complete the second composition (B). , With respect to 100 parts by weight (100 g) of a water-soluble polymer aqueous solution, 2.2 g of citric acid was dissolved in 1.5 parts by weight of CMC in an aqueous solution, mixed with the secondary composition (B), and stirred at 500 ppm or less for 1 hour to prepare a laminate coating composition. , Was measured as in Example 1 (see Table 4).

< Comparative example 3>

5 parts by weight of natural zeolite crushed stone with an average particle diameter of 200 nanometers in another adsorbent, except for sodium chlorite and citric acid, which are involved in the mechanism of chlorine dioxide generation, and 6 parts by weight of diatomaceous earth with a pore size of 5 to 100 nm, 3 parts by weight of talc After preparing an adsorbent of 5 parts by weight of light (parts by weight of adsorbent to 100 parts by weight of water-soluble polymer solution), 0.6 parts by weight of dispersant was added to 1.5 parts by weight of CMC aqueous solution based on 100 parts by weight of water-soluble polymer aqueous solution. After mixing eggplants in order and stirring at room temperature at 1000 rpm or less for 1 hour or more to form the first composition (A), 4 parts by weight of a glycidyl-based acrylic resin adhesive was mixed with respect to 100 parts by weight of the first composition, and an alcohol-based defoaming agent After adding 0.4 parts by weight to the first composition, stirring at 500 rpm or less for 60 minutes or more to complete the second composition (B), and then 1.5 parts by weight of CMC aqueous solution was added to 100 parts by weight of the water-soluble polymer aqueous solution, and 1 at 500 rpm or less. A layered coating composition was prepared by stirring for a period of time, and it was measured as in Example 1.

Table 5 shows the pore diameter, particle size, input amount, and chlorine dioxide generation used in Examples 3 to 5.

The results of the formaldehyde removal experiment in Examples 3 to 5 are as follows (see Table 5).

Table 6 shows the measured values of formaldehyde and VOCs over 5 hours.

As described above, the laminated coating agent of the present invention is for a composition that adsorbs, decomposes, and shields formaldehyde released from artificial plate adhesives such as plywood, particle board, and medium-density fiberboard. It is a liquid composition that adsorbs, decomposes, and shields formaldehyde continuously released from furniture, desk drawers, wardrobes, windows, shelves, cupboards, and sinks that are exposed without finishing treatment. have.

Accordingly, the present invention purifies the quality of indoor air by adsorbing, decomposing, and shielding formaldehyde, which is a harmful substance generated from artificial plate, to remove substances harmful to the human body, and thus construction materials, adhesives, wallpaper, and materials used in new buildings or new furniture. Volatile organic compounds and harmful substances generated from paints are prevented from causing unpleasant feelings of health and indoor life of residents to maintain a healthy and comfortable living space.

10: artificial plate 11: formaldehyde generation
21: alumina silicate 22: diatomaceous earth
23: chlorine dioxide 34: laminated coating composition surface

Claims (7)

Preparing a heterogeneous porous first adsorbent⒜ composed of aluminum silicate having 4-8 angstrom pores capable of adsorbing formaldehyde; and
Preparing a heterogeneous porous second adsorbent⒝ and a dispersant composed of diatomaceous earth, talc, and illite having a pore size of 5 to 100 nm, and
After the first adsorbent ⒜ made of aluminum silicate is supported in a water-soluble polymer aqueous solution, chlorite is permeated into the pores of the aluminum silicate, and then the second adsorbent ⒝ is sequentially mixed, and a polymer resin adhesive of glycidyl acrylic resin is added. Constituting the composition (A),
A secondary composition (B) is formed by adding an additive consisting of a thickener, an antifoaming agent, and a fluidizing agent that can adjust the work properties according to the use of the primary composition (A),
Form released from an artificial plate, characterized in that a coating solution composition is prepared by mixing 100 g of a water-soluble polymer aqueous solution in which 1.25 g of chlorite, a precursor of chlorine dioxide, is dissolved separately, and the prepared first composition (A) or second composition (B) is mixed. A method for producing a chlorine dioxide sustained-release laminated coating liquid composition for adsorbing and decomposing aldehydes. The composition prepared by the method for producing a chlorine dioxide sustained-release layered coating liquid composition that adsorbs and decomposes formaldehyde released from an artificial plate,
A water-soluble polymer aqueous solution is supported by a dissimilar porous first adsorbent ⒜ made of aluminum silicate, and chlorite is permeated into the pores of the aluminum silicate, and then dissimilar porous second adsorbent ⒝ is sequentially mixed. The primary composition (A) to which a polymer resin adhesive of cidyl acrylic resin was added, and
A secondary composition (B) in which additives consisting of a thickener, an antifoaming agent, and a fluidizing agent are added to the primary composition (A), which can adjust the working properties according to the use, and
After preparing the first composition or the second composition, a water-soluble polymer aqueous solution ⒜100 g in which 1.25 g of chlorite, which is a chlorine dioxide precursor, is dissolved separately is mixed with the prepared first composition (A) or the second composition (B) to obtain Chlorine dioxide sustained-release laminated coating liquid composition that adsorbs and decomposes formaldehyde released from an artificial plate, characterized in that chlorine-activating chlorine dioxide sustained-release laminated coating liquid composition. The method of claim 2,
Chlorine dioxide sustained-release lamination that adsorbs and decomposes formaldehyde emitted from an artificial plate characterized by dissolving in a water-soluble polymer material by selecting one of sodium chlorite, calcium chlorite, and lithium chlorite as precursors to generate chlorine dioxide Coating liquid composition. The method of claim 2,
Chlorine dioxide that adsorbs and decomposes formaldehyde released from artificial plates, characterized by dissolving one of agar, hydroxypropylmethylcellulose, starch, and carginane as a water-soluble polymer material that acts as a reaction delay buffer and activator. Release lamination coating liquid composition. The method of claim 2,
For this type of adsorbent, select one type from bentonite, silica gel, moderite, zeolite, sepiolite, and aluminum silicate, and the average particle diameter must be 4 microns or less, and the particles have a micropore of 8Å (angstrom) or less. The first adsorbent ⒜ and a type of amorphous second adsorbent ⒝ having a large pore of 5 to 100 nm among adsorbents such as morderite, bentonite, sepiolite, diatomaceous earth, and loess, and heavy calcium carbonate, talc, chlorite, hard carbonic acid for fluid physical properties. Chlorine dioxide that adsorbs and decomposes formaldehyde released from artificial plates characterized by dispersing and supporting a type of third adsorbent⒞ selected from calcium, titanium oxide, and illite in a chlorite-soluble polymer material in sequence at 1000 rpm for more than 60 minutes. Release lamination coating liquid composition. The method of claim 2,
At least one selected from styrene-butadiene/nitrile-butadiene latex, polyvinyl alcohol, polyvinyl acetate, ethyl vinyl acetate, urethane resin, and acrylic resin, which are heterogeneous adsorbents dispersed and supported in chlorite-soluble polymer materials and polymer resin composites. Chlorine dioxide sustained-release lamination coating composition for adsorbing and decomposing formaldehyde released from an artificial plate by mixing and stirring at 500 rpm for at least 60 minutes. The method of claim 2,
Adsorption of formaldehyde emitted from an artificial plate, characterized in that after introducing a kind selected from mineral-based, silicone-based, and alcohol-based antifoaming agents and polyacrylic acid-based and phosphate-based dispersants for the laminated coating properties, and stirred at 500 rpm or less for 60 minutes or longer. Decomposing chlorine dioxide sustained-release lamination coating liquid composition.

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