KR102284172B1 - Surface hardner composition for inhibiting scattering dust and method for manufacturing the same - Google Patents

Abstract

The present invention relates to a surface curing agent for suppressing scattering dust and a method for manufacturing the same. The present invention provides a surface curing agent that suppresses scattering dust by forming a film on an object to be treated and includes hydrophilic polymers, cross-linked polymers, surfactants and water, and a method for manufacturing the same. The cross-linked polymer includes a cross-linked product that is formed by cross-linking at least one selected from polyvinyl alcohol and gum by a cross-linking agent. According to the present invention, after being sprayed on an object to be treated such as soil, wood flour, lime, ash, coke and/or coal and the like, the surface curing agent has excellent scattering dust suppression effect and durability by forming a water-resistant strong cured film, prevents from flowing down even in the rainy season or rain, is harmless to a human body, and is eco-friendly.

Description

Surface hardener for suppressing scattering dust and its manufacturing method

The present invention relates to a surface hardener for suppressing scattering dust such as fine dust and a method for manufacturing the same, for example, by forming a hardened film on the surface of soil, wood flour, lime, ash, coke and/or coal, etc. to at least scatter It relates to a surface hardener having excellent dust suppression effect and improved water resistance and durability (sustainability of scattering dust suppression), and a method for manufacturing the same.

Fugitive dust is generated not only on general roads, but also in almost the entire human living area, such as various industrial sites. Fugitive dust is generated in large amounts, for example, in factories (yards), playgrounds, mines, road construction sites and construction sites such as earth and sand, wood flour, lime, ash, coke, coal, cement and aggregates.

Fugitive dust is a particulate matter that floats or is blown down in the atmosphere, and is also called scattering dust or flying dust. Fugitive dust floating in the air contains micro-dust, which is classified according to particle size (diameter).

In general, TSP (Total Suspended Particles) is for dust with a size of 50 μm or less floating in the atmosphere, PM10 (Particulate Matter 10) for fine dust with a size of 10 μm or less, and PM2.5 (Particulate Matter) for ultra-fine dust with a size of 2.5 μm or less. 2.5). In particular, fine dust of 10 μm or less is small enough to be invisible, so it can easily enter the body through the respiratory system. Fine dust introduced into the body is deposited in the bronchial or alveolar area, lowering the function of the lungs and lowering the immune function of the human body.

As a method of suppressing scattering dust, the method of spraying (sprinkling) water is typical, and this is the cheapest method. However, spraying water has a lower effect of suppressing scattering dust compared to the amount of water used, and in winter, it freezes after spraying, increasing the risk of falls, etc. . In addition, a method of covering a dust barrier is used to suppress scattering dust in yards such as soil or coal, but the dust barrier has a problem in that installation work is cumbersome and is easily peeled off by strong winds.

Accordingly, various methods for suppressing scattering dust have been proposed, and a representative method of spraying the scattering dust inhibitor is a method. The scattering dust inhibitor has advantages such as at least the scattering dust suppression effect and durability compared to water spray. In general, the scattering dust inhibitor contains an inorganic compound such as calcium carbonate or a polymer such as a vinyl acetate copolymer as an active ingredient (main component).

For example, Korean Patent No. 10-0494538, Korean Patent No. 10-1057107, Korean Patent No. 10-1293257, Korean Patent No. 10-1881402, Korean Patent Publication No. 10-2014-0078594 No. and Japanese Patent Laid-Open No. 2009-035647, etc. have proposed the above related technology.

However, the scattering dust inhibitor according to the prior art has, for example, the following problems.

First, inorganic compounds have a weak cohesive ability of scattering dust, so the effect of suppressing scattering dust is low compared to the amount used. In addition, when calcium carbonate is used as an inorganic compound, there is a risk of ignition and environmental problems such as acidification of the soil. In addition, the vinyl acetate copolymer is a polymer obtained by emulsion polymerization or solution polymerization of a vinyl acetate monomer, which does not cause soil acidification, but has a disadvantage in poor water resistance.

As described above, the scattering dust inhibitor according to the prior art has ignition generation and environmental problems, or has weak water resistance, so it is vulnerable to the rainy season or rainfall. In addition, the scattering dust inhibitor according to the prior art forms a weak film and is weak to ultraviolet rays, so there is a problem in that durability (continuity of the scattering dust suppression effect), etc. is low.

Korean Patent Registration No. 10-0494538 Korean Patent Registration No. 10-1057107 Korean Patent Registration No. 10-1293257 Korean Patent Registration No. 10-1881402 Korean Patent Publication No. 10-2014-0078594 Japanese Patent Laid-Open No. 2009-035647

Accordingly, an object of the present invention is to provide a surface hardener that can be usefully used as a scattering dust inhibitor and a method for manufacturing the same.

Specifically, the present invention forms a strong hardened film after being sprayed on the object to be treated, such as soil, wood flour, lime, ash, coke and/or coal, and has excellent scattering dust suppression ability, water resistance and durability (of the scattering dust suppression effect) It is an object of the present invention to provide a surface hardener and a method for manufacturing the same for improved scattering dust suppression.

In order to achieve the above object, the present invention

As a surface hardener that forms a film on the object to be treated and suppresses scattering dust,

hydrophilic polymers;

crosslinked polymers;

Surfactants; and

A surface curing agent comprising water is provided.

According to one embodiment, the cross-linked polymer includes a cross-linked product cross-linked by at least one selected from polyvinyl alcohol and gums by a cross-linking agent. In this case, the crosslinked polymer (crosslinked product) has an ether (-O-) bond.

In addition, the present invention,

reacting at least one selected from polyvinyl alcohol and gums with a crosslinking agent to produce a crosslinked polymer crosslinked by at least one selected from polyvinyl alcohol and gums by a crosslinking agent; and

It provides a method for producing a surface curing agent comprising the step of mixing a hydrophilic polymer, a surfactant and water to the crosslinked polymer.

According to one embodiment, the crosslinking agent may include a compound having an epoxy group and a halogen group. In addition, the reaction may be carried out under alkaline conditions of pH 9 to 12.

According to the present invention, there is provided a surface curing agent that can be usefully used as a scattering dust inhibitor and has improved scattering dust suppression ability, water resistance and durability, and a method for manufacturing the same.

Specifically, the present invention forms a strong water-resistant hardened film after being sprayed on a target object such as soil, wood flour, lime, ash, coke, and/or coal, so that it has excellent scattering dust suppression ability and can flow down even in the rainy season or rain. has a preventive effect.

In addition, the present invention has the effect of improving the durability of the suppression of scattering dust due to strong UV resistance and excellent durability. In addition, it is environmentally friendly as it is harmless to the human body or soil.

1 is a schematic view showing a process of forming a cured film after the surface curing agent according to the present invention is sprayed on a target object.
2 is a photograph showing a test overview and a test view according to an embodiment of the present invention.
3 is a photograph of each sample showing a state in which 24 hours have elapsed after the surface curing agent is sprayed according to an embodiment of the present invention.
4 is a graph showing the results of the scattering dust suppression ability evaluation (the ratio of scattering dust compared to the control group) according to an embodiment of the present invention.
5 is a graph showing the evaluation result (reduction efficiency compared to water injection) of scattering dust suppression ability according to an embodiment of the present invention.
6 is a photograph showing a measurement location of each area in the field evaluation according to an embodiment of the present invention.
7 is a photograph showing the state of measurement of each area in the field evaluation according to an embodiment of the present invention.
8 to 12 are graphs showing the results of fine dust measurement according to the passage of time (date) for each region.

The term "and/or" as used in the present invention is used to mean including at least one or more of the components listed before and after. As used herein, the term “one or more” refers to one or a plurality of two or more.

The present invention provides a surface hardener (or scattering dust inhibitor) that effectively suppresses scattering dust by forming a film after being sprayed on a target object. In addition, the present invention provides a method for producing the surface curing agent. In the present invention, "scattering dust" includes fine dust, pollen, etc. as well as general dust floating in the atmosphere. In the present invention, "scattering dust" includes, for example, coal powder, stone powder, earth powder, gypsum powder, cement powder, concrete powder, pollen and/or smoke.

In addition, in the present invention, the object to be treated, that is, the object to which the surface curing agent (scattering dust inhibitor) according to the present invention is applied, is the object to be treated in which scattering dust (dust) is generated, and/or scattering Includes the object to be treated on which dust (dust) is to be generated. The to-be-processed object is, for example, yards, such as earth and sand, wood powder, lime, ash, coke, coal, iron making, concrete, and a cement factory; various storage materials such as mines, construction sites and road construction sites; road; Playground; and/or other loose land where dust is scattered by wind; and the like. Hereinafter, in the description of the present invention, the object to be treated will be described by taking as an example a yard such as soil or coal in some cases.

The surface curing agent according to the present invention is a scattering dust suppression composition that suppresses scattering dust, and includes a hydrophilic polymer; crosslinked polymers (crosslinked products); Surfactants; and water. The surface hardener according to the present invention is sprayed on a target object (a yard) such as soil or coal to form a thin cured film on the surface of soil or coal to suppress scattering of dust. 1 is a schematic view showing a process in which a cured film is formed after being sprayed onto an object to be treated.

In addition, the method for producing a surface curing agent according to the present invention comprises the steps of generating (synthesizing) a cross-linked polymer (cross-linked product); and mixing a hydrophilic polymer, a surfactant, and water with the crosslinked polymer (crosslinked product). Hereinafter, exemplary embodiments of the present invention will be described.

[1] Hydrophilic polymer

The hydrophilic polymer acts as an active ingredient (film-forming agent) for forming a cured film. The hydrophilic polymer is not particularly limited as long as it is hydrophilic (water-soluble) and capable of forming a cured film on the surface of soil, lime, ash, coke and/or coal. The hydrophilic polymer may be selected from, for example, a vinyl acetate copolymer and a polyacrylate-based polymer.

According to a preferred embodiment, the hydrophilic polymer comprises a modified vinyl acetate copolymer. The modified vinyl acetate copolymer is a vinyl acetate-acrylate copolymer copolymerized with vinyl acetate and acrylate, and/or the vinyl acetate-acrylate copolymer has ions It may include an ionic vinyl acetate-acrylate copolymer with added properties.

The modified vinyl acetate copolymer is preferable in the present invention because it has advantages in scattering dust suppression ability, quick-drying property and water resistance, etc., than the vinyl acetate copolymer. In addition, in the case of the ionic vinyl acetate-acrylate copolymer, it also has the ability to suppress the generation of static electricity, so it is preferable in the present invention. The ionic vinyl acetate-acrylate copolymer may have ionicity by coordinating metal ions such as Mg, Na, K and/or Ca to vinyl acetate-acrylate. This ionic vinyl acetate-acrylate copolymer has the ability to suppress the generation of static electricity due to ionicity, and can prevent spontaneous ignition that may be caused by static electricity when applied to an object to be treated, such as coal.

The hydrophilic polymer is not particularly limited, but may be included, for example, in an amount of 5 to 60% by weight, based on the total weight of the surface curing agent according to the present invention. At this time, when the content of the hydrophilic polymer is less than 5% by weight, it may be difficult to form a strong cured film. In addition, when the content of the hydrophilic polymer exceeds 60% by weight, compounding workability may be deteriorated, and the content of the cross-linked polymer or surfactant may be relatively low. In consideration of this, the hydrophilic polymer is preferably included in an amount of 6 to 50% by weight, 6 to 40% by weight, or 8 to 35% by weight based on the total weight of the surface curing agent according to the present invention.

[2] Cross-linked polymer

The cross-linked polymer is selected from a cross-linked product cross-linked by at least one selected from polyvinyl alcohol (PVA) and gum. This crosslinked polymer (crosslinked product) acts as an active ingredient (film forming agent) for forming a cured film together with the hydrophilic polymer. That is, the surface curing agent according to the present invention is a film forming agent for forming a cured film, and includes the hydrophilic polymer (eg, modified vinyl acetate copolymer) and a crosslinked polymer (crosslinked product).

According to the present invention, when the cross-linked polymer is further included as a film-forming agent, it is effective in suppressing scattering dust by forming a stronger cured film than when using the hydrophilic polymer alone. In particular, according to the present invention, the water resistance and durability of the cured film are effectively improved by the cross-linked polymer. Accordingly, not only is the scattering dust suppression better than when the hydrophilic polymer is used alone, it is also prevented from flowing down during the rainy season or rain, and the durability of the scattering dust suppression ability is improved.

The gum may be selected from natural polymers (polysaccharides) having -OH groups in the molecule, for example, Xanthan gum, Agar gum, Guar gum, Tara gum) and at least one selected from locust bean gum and the like. The gum is preferably _{selected from natural polymers (polysaccharides) having -OH and -CH 2} 0H groups in the molecule, and may include, for example, Xanthan gum.

The crosslinking agent is capable of crosslinking between polyvinyl alcohol (PVA), crosslinking between gums, and/or crosslinking between polyvinyl alcohol (PVA) and gum, which is selected from compounds having an epoxy group and a halogen group do. The crosslinking agent may include, for example _{, at least one selected from epichlorohydrin (C 3} H ₅ ClO), epibromohydrin (C ₃ H ₅ BrO), and derivatives thereof.

In the present invention, the cross-linked polymer is a hydrophilic cross-linked product in which polyvinyl alcohol and/or gum are cross-linked by a cross-linking agent, which is a cross-linked product between polyvinyl alcohol; cross-linked products between gums; and at least one selected from a cross-linked product of polyvinyl alcohol and gum. When polyvinyl alcohol is 'PVA', xanthan gum is 'XG' as an example of a gum, and epichlorohydrin is 'ECH' as an example of a crosslinking agent, the crosslinked polymer is PVA-ECH in which PVA and PVA are crosslinked by ECH. -PVA crosslinked product; XG-ECH-XG crosslinked product in which XG and XG are crosslinked by ECH; and PVA-ECH-XG crosslinked products in which PVA and XG are crosslinked by ECH. Each of these crosslinked products is a derivative of PVA, a derivative of XG or a derivative of PVA-XG. According to a preferred embodiment, the cross-linked polymer is a cross-linked product of polyvinyl alcohol and gum, and a polyvinyl alcohol-gum cross-linked product (eg, PVA-ECH-XG cross-linked) in which polyvinyl alcohol and gum are cross-linked with epichlorohydrin. water) may be included.

Further, according to a preferred embodiment of the present invention, the cross-linked polymer may be selected from etherified derivatives having an ether (-O-) bond. Specifically, it is preferable that at least one selected from polyvinyl alcohol and gums and the crosslinking agent have an ether (-O-) bond. For example, in the PVA-ECH-XG cross-linked product (derivative of PVA-XG), PVA and ECH are ether (-O-) bonded, and ECH and XG are also ether (-O-) bonded to cross-linked PVA It is preferably an etherified derivative of -XG. The crosslinked polymer may include, for example, a repeating unit represented by the following [Formula 1].

[Formula 1]

R ¹ -OCOR ²

In [Formula 1], R ¹ and R ² are the same as or different from each other, and are each independently a derivative derived from polyvinyl alcohol and gums. In addition, in [Formula 1], C is derived from a crosslinking agent, which is a derivative of epichlorohydrin or epibromohydrin. As shown in [Formula 1], R ¹ and C, and C and R ² may be cross-linked by an ether (-O-) bond. The crosslinked polymer may have a weight average molecular weight of, for example, 20,000 to 1,000,000, or 50,000 to 800,000, including the compound of [Formula 1].

According to the present invention, when the cross-linked polymer has an ether (-O-) bond at the binding site with the cross-linking agent, chemical and mechanical properties can be improved. For example, when a binding site with a crosslinking agent has an ester (-COO-) bond, it may be unstable, resulting in lower chemical and mechanical properties. In contrast, in the case of having an ether (-O-) bond, the chemical and mechanical properties are improved, so that it is more effective in suppressing scattering dust than in the case of having an ester (-COO-) bond, and viscoelasticity, water resistance, acid resistance and durability are improved. In addition, the ether (-O-) bond does not gel thixotropy, so it has long-term storage, and has UV resistance and heat resistance.

Meanwhile, the cross-linked polymer (cross-linked product) may be produced (synthesized) by reacting at least one selected from polyvinyl alcohol and gum with a cross-linking agent at a predetermined temperature. For example, the polyvinyl alcohol-gum cross-linked product (eg, PVA-ECH-XG cross-linked product) may be produced (synthesized) by reacting polyvinyl alcohol, a gum, and a cross-linking agent at a predetermined temperature.

In another example, the polyvinyl alcohol-gum cross-linked product (eg, PVA-ECH-XG cross-linked product) is prepared by first reacting a gum with a cross-linking agent to obtain a gum-cross-linking agent (intermediate) in which a gum and a cross-linking agent are combined. Then, polyvinyl alcohol is added and reacted to the gum-crosslinking agent (intermediate) to produce (synthesize) polyvinyl alcohol-gum crosslinked product.

In the above synthesis reaction, the amount of the crosslinking agent to be used is not particularly limited. The crosslinking agent may be used in an amount of, for example, 0.1 to 60 parts by weight, 0.2 to 50 parts by weight, or 0.5 to 40 parts by weight, based on 100 parts by weight of polyvinyl alcohol and/or gum, but is not limited thereto.

Each of the above reactions may be carried out, for example, at a temperature of 60° C. to 80° C. for about 3 hours to 8 hours. In addition, each of the above reactions may be carried out under alkaline conditions of pH 9 to 12. In this case, the alkaline conditions include, for example, alkaline solutions such as NaOH and/or KOH. For example, when synthesizing the polyvinyl alcohol-gum cross-linked product, polyvinyl alcohol, gum, and a cross-linking agent are added to an alkaline solution (eg, NaOH aqueous solution) at a temperature of about 60° C. to 80° C. for 3 hours It can be synthesized by crosslinking reaction for 8 hours.

According to an embodiment of the present invention, the crosslinking agent is a compound having an epoxy group and a halogen group, and at least one selected from epichlorohydrin and epibromohydrin is used, and during the reaction, the reaction is carried out under alkaline conditions of pH 9 to 12. , preferred for the synthesis of etherified derivatives advantageous in chemical and mechanical properties. That is, a cross-linked polymer (eg, an etherified derivative of PVA-XG) having an ether (-O-) bond at the binding site with the cross-linking agent can be synthesized in high yield.

The etherified derivative as the cross-linked polymer may be synthesized, for example, through the following [Formula 2] and [Formula 3]. [Formula 2] illustrates the synthesis of xanthan gum (XG) etherified derivatives, and [Formula 3] illustrates the synthesis of polyvinyl alcohol (PVA)-xanthan gum (XG) etherified derivatives. . In the following [Formula 2] and [Formula 3], n is an integer. n is not particularly limited, but may be, for example, an integer of 100 to 5,000, and may be, for example, an integer of 500 to 3,000. In addition, in the following [Formula 2] and [Formula 3], * is a connection point.

Referring to [Formula 2], when xanthan gum (XG) and epichlorohydrin (ECH) are reacted under alkaline conditions (NaOH), an intermediate (XG'-O-ECH') in which ECH' is bonded to XG' is obtained. generated, and then an XG etherified derivative (XG'-O-ECH'-O-XG') in which XG' is bonded to the intermediate (XG'-O-ECH') can be synthesized by a series of reactions. In this case, XG' means a derivative of XG, and ECH' means a derivative of ECH. As shown in [Formula 2], XG' and ECH' have an ether (-O-) bond.

[Formula 2]

In addition, referring to the following [Formula 3], first, when xanthan gum (XG) and epichlorohydrin (ECH) are reacted under alkaline conditions (NaOH), an intermediate in which ECH' is bonded to XG' (XG'-O- ECH') is generated. Then, when polyvinyl alcohol (PVA) is further added and reacted under alkaline conditions (NaOH), PVA-XG etherified derivative (PVA'-O-) in which PVA' is bonded to the intermediate (XG'-O-ECH') ECH'-O-XG') can be synthesized. In this case, PVA' means a derivative of PVA, XG' means a derivative of XG, and ECH' means a derivative of ECH. As shown in the following [Formula 3], PVA' and ECH' have an ether (-O-) bond, and ECH' and XG' also have an ether (-O-) bond.

[Formula 3]

As shown in [Formula 2] and [Formula 3], polyvinyl alcohol (PVA) and/or xanthan gum (XG) is cross-linked by a cross-linking agent (ECH) having an epoxy group and a halogen group, but a cross-linking agent (ECH) It has an ether (-O-) bond at its binding site. For example, in the case of an etherified derivative of PVA-XG (Formula 3), an epoxy group present on one side of the crosslinking agent (ECH) forms an ether (-O-) bond with XG, and exists on the other side of the crosslinking agent (ECH) As the halogen group (Cl) is desorbed, PVA is ether (-O-) bonded thereto. Therefore, when a compound having an epoxy group and a halogen group is used as a crosslinking agent, it is useful for the synthesis of a crosslinked product having an ether (-O-) bond (for example, an etherified derivative of PVA-XG), which also has a high yield. have

According to the present invention, the cross-linked polymer (preferably, a cross-linked product having an ether (-O-) bond) is mixed with a hydrophilic polymer to effectively suppress various scattering dust and maintain a cured film for a long time to maintain the scattering dust suppression ability this is high In particular, it forms a water-resistant, strong cured film to prevent collapse or run-down due to rain or strong wind. In addition, the cross-linked polymer is harmless to the human body and environment-friendly, for example, forms a stronger film than a simple natural polymer (non-cross-linked natural polymer) or synthetic polymer, and has excellent corrosion resistance, moisture retention and weather resistance.

The cross-linked polymer is not particularly limited, but may be included in an amount of, for example, 2 to 40% by weight, based on the weight of the surface curing agent according to the present invention. In this case, when the content of the crosslinked polymer is less than 2% by weight, the improvement effect such as water resistance and durability according to its use may be low. And when the content of the crosslinked polymer exceeds 40% by weight, for example, the viscosity may increase and workability may be deteriorated during the compounding process. In consideration of this, the cross-linked polymer is preferably included in an amount of 3 to 35% by weight, 5 to 35% by weight, or 5 to 30% by weight based on the weight of the surface curing agent according to the present invention.

[3] Surfactant

The surfactant is for dispersing and emulsifying, and it imparts permeability and wettability (moisture) to the surface of soil, wood flour, lime, ash, coke and/or coal, etc., and each component (hydrophilic polymer and cross-linked polymer) etc.) is not particularly limited as long as it has dispersibility between the two.

As the surfactant, a water-soluble natural surfactant may be used, and for example, a nonionic surfactant may be usefully used. When a nonionic surfactant is used as the natural surfactant, it is preferable to have wettability and improve permeability and dispersibility to the object to be treated. The natural surfactant, for example, may be selected from polyoxyethylenes, sorbitans and/or glucosides, preferably sorbitan monooleate, sorbitan monolaurate, lauryl glycoside and At least one selected from decylglycoside and the like may be usefully used.

The surfactant may be included in an amount of, for example, 1 to 12% by weight, based on the total weight of the surface curing agent according to the present invention. At this time, when the content of the surfactant is less than 1% by weight, the surface permeability, wettability maintenance and dispersibility improvement effect according to the addition thereof may be lowered. And when the content of the surfactant exceeds 12% by weight, foam or the like may be generated to interfere with the formation of a strong cured film. Considering this point, the surfactant is preferably included in an amount of 2 to 10% by weight, or 3 to 8% by weight, based on the total weight of the surface curing agent according to the present invention.

[4] water

The water is used as a dispersing and/or diluting solvent, and for example, tap water, distilled water, groundwater and/or purified water may be used. Water may be included in, for example, 5 to 50% by weight, 10 to 40% by weight, or 10 to 35% by weight based on the total weight of the surface curing agent according to the present invention, but is not limited thereto.

[5] Additional ingredients

In addition, the surface curing agent according to the present invention may further include additional components such as functional components or additives in addition to the above components. The surface curing agent according to the present invention may further include one or more functional ingredients from, for example, a moisturizing agent, a coloring agent, and an antistatic generation inhibitor. These functional ingredients can be used by selecting from ingredients that do not reduce the scattering dust suppression ability.

The humectant is for maintaining the continuity of moisture, and may be selected from water-soluble humectants. The moisturizer is preferably an eco-friendly material, and for example, at least one selected from hyaluronic acid, plant-derived glycerin, coconut oil, shea butter, camellia oil and sorbitol may be used, but is not limited thereto.

The humectant may be included in an amount of, for example, 0.5 to 12% by weight, based on the total weight of the surface curing agent according to the present invention. At this time, when the content of the moisturizing agent is less than 0.5% by weight, the degree of improvement in moisturizing according to the addition thereof may be insignificant. And when the content of the humectant exceeds 12% by weight, it may be difficult to form a good cured film because the content of the hydrophilic polymer and/or the cross-linked polymer is relatively low.

The coloring agent is for forming a colored cured film, and may be selected from water-soluble colored forming materials. The coloring agent may be selected from pigments and/or pigments having a color.

The coloring agent may be selected from those capable of forming a colored cured film such as white, blue, or green (green mint), for example. After being sprayed onto the object to be treated by such a colored agent, it can have visibility that can be visually checked. Accordingly, the presence or absence of injection can be visually checked, thereby preventing excessive injection or overlapping injection. The coloring agent may be included in an amount of, for example, 0.5 to 10% by weight, based on the total weight of the surface curing agent according to the present invention.

The static electricity generation inhibitor is not particularly limited as long as it can prevent static electricity generation. When such a static electricity generation inhibitor is added, it can be usefully applied to an object to be treated, such as coal, which has a high rate of spontaneous ignition. The static electricity generation inhibitor is, for example, behentrimonium methosulfate, cetrimonium methosulfate, behenyl trimethyl ammonium methosulfate (Behenyl trimethyl ammonium methosulfate) and / or steartrimonium methosulfate ( Steartrimonium methosulfate) and the like may be usefully selected from one or more. The static electricity generation inhibitor may be included, for example, in an amount of 0.1 to 10% by weight, based on the total weight of the surface curing agent according to the present invention.

According to a preferred embodiment, it is preferable to use at least one selected from among the components listed above as the static electricity generation inhibitor from among Cetrimonium methosulfate and Steartrimonium methosulfate. In addition, the surface curing agent according to the present invention may further include 3-carboxy-1-adamantane acetic acid as an activator of the antistatic agent.

According to a preferred embodiment of the present invention, when cetrimonium methosulfate and steartrimonium methosulfate are used as static electricity generation inhibitors, it is more effective in inhibiting static electricity generation than when other antistatic agents are used. In addition, the 3-carboxy-1-adamantane acetic acid effectively activates the cetrimonium methosulfate and steartrimonium methosulfate as static electricity generation inhibitors to improve the static electricity generation inhibitory ability. Specifically, the 3-carboxy-1-adamantane acetic acid can have excellent static electricity generation suppression ability by increasing the activity of the static electricity generation inhibitor even when a small amount of the static electricity generation inhibitor is used. At this time, the surface curing agent according to the present invention may include 0.5 to 5% by weight of an antistatic agent selected from the cetrimonium methosulfate and/or steartrimonium methosulfate, based on the total weight, and the 3-carboxy-1 -Adamantane acetic acid may be included in an amount of 0.1 to 3% by weight.

In addition, the surface curing agent according to the present invention may further include one or more additives selected from a dispersant, a cryoprotectant, an antifoaming agent, a storage stabilizer, a viscosity modifier, and the like, if necessary. These additives may be selected from those commonly used, and may be added in an appropriate amount in a range that does not reduce the ability to suppress scattering dust. The additive may be included in an amount of, for example, 0.001 to 10% by weight or 0.01 to 5% by weight, based on the total weight of the surface curing agent according to the present invention.

The surface hardener according to the present invention described above forms a hardened film on the surface of the object to be treated, such as soil or coal, to suppress scattering of dust, and maintains moisture (durability) for a long time due to high moisture and wettability, thereby suppressing scattering. have a lasting effect. In addition, it has excellent water resistance, acid resistance and UV resistance while forming a strong cured film. In addition, workability is improved as a quick-drying property, has harmless to human body and environment-friendly characteristics, and spontaneous combustion of coal powder is prevented, thereby preventing coal loss and fire.

On the other hand, when the surface curing agent according to the present invention is applied to the object to be treated, for example, it can be applied through a method such as spraying. At this time, when applying by the spray method, dilute it in separate water and use it. According to one embodiment, the surface curing agent according to the present invention can be used by diluting water in a weight ratio (or volume ratio) of 5 to 100 times, and spraying (spraying) on the object to be treated. Specifically, a treatment solution (diluent) diluted in a weight ratio (or volume ratio) of the surface curing agent of the present invention: water = 1: 5 to 100 is obtained, and then the treatment solution (diluent) is sprayed with a spraying device (eg, a sprinkler, etc.) ) can be used as a method of forming a cured film by spraying (spraying) on the object to be treated.

Hereinafter, Synthesis Examples, Examples and Comparative Examples of the present invention are exemplified. The following synthesis examples and examples are provided for illustrative purposes only to help the understanding of the present invention, and the technical scope of the present invention is not limited thereby. In addition, the following comparative examples do not mean the prior art, and are provided only for comparison with the examples.

<Synthesis Example 1> Synthesis of crosslinked polymer (Synthesis of etherified crosslinked product of PVA-XG)

NaOH aqueous solution and degreased xanthan gum (XG) powder were put in a reactor, epichlorohydrin (ECH) was added thereto as a crosslinking agent, and reacted at about 75° C. for 5 hours under alkaline conditions (NaOH aqueous solution) of pH 10.8. Thereafter, polyvinyl alcohol (PVA) was further added to the reactor, and then reacted under alkaline conditions (NaOH aqueous solution) at about 65° C. for 4 hours to prepare a cross-linked polymer synthesis solution including a PVA-XG cross-linked product. In this case, the PVA-XG crosslinked product is a crosslinked product of PVA and XG by ECH under alkaline conditions (NaOH aqueous solution), which is an etherified derivative of PVA-XG in which PVA and ECH are ether-bonded and XG and ECH are also ether-bonded. (PVA-et-XG).

<Synthesis Example 2> Synthesis of cross-linked polymer (Synthesis of cross-linked esterification product of PVA-XG)

An aqueous acetic acid solution and degreased xanthan gum (XG) powder were placed in a reactor, epichlorohydrin (ECH) was added thereto as a crosslinking agent, and reacted at about 75° C. for 5 hours under acidic conditions of pH 5.4 (acetic acid aqueous solution). Thereafter, polyvinyl alcohol (PVA) was further added to the reactor, and then reacted under acidic conditions (aqueous acetic acid solution) at about 65° C. for 4 hours to prepare a cross-linked polymer synthesis solution containing a PVA-XG cross-linked product. In this case, the PVA-XG crosslinked product is a crosslinked product in which PVA and XG are crosslinked by ECH under acidic conditions (aqueous acetic acid solution), which is an esterified derivative of PVA-XG in which PVA and ECH are ester-bonded and XG and ECH are also ester-bonded. (PVA-est-XG).

[Example 1]

A small amount of water (distilled water) was put into a container with a different stirrer, and the crosslinked polymer synthesis solution synthesized in Synthesis Example 1 (etherified crosslinked product of PVA-XG) was added thereto. Thereafter, an appropriate amount of a hydrophilic polymer, a surfactant, a moisturizing agent, and a dispersing agent was added and stirred. At this time, the hydrophilic polymer is a vinyl acetate-acrylate copolymer synthesized from a copolymerizable solution containing vinyl acetate, 2-ethylhexyl acrylate, hydroxyethyl acrylate and acrylic acid, which was purchased from Eastwood Chemical in Korea and used. . Sorbitan monolaurate was used as the surfactant, hyaluronic acid and vegetable glycerin were used as the moisturizing agent, and Span 80 was used as the dispersing agent. Specific components and contents of the surface curing agent according to this Example are shown in Table 1 below. In [Table 1] below, the content of each component is a percentage (wt%) based on the total weight of the surface curing agent.

[Example 2]

A surface curing agent according to this example was prepared in the same manner as in Example 1, except that the crosslinked polymer synthesized in Synthesis Example 2 (esterified crosslinked product of PVA-XG) was used. Specific components and contents of the surface curing agent according to this Example are shown in Table 1 below.

[Example 3]

A surface curing agent according to this example was prepared in the same manner as in Example 1, except that a vinyl acetate copolymer was used as the hydrophilic polymer. Specific components and contents of the surface curing agent according to this Example are shown in Table 1 below.

[Comparative Example 1]

A surface curing agent according to Comparative Example was prepared in the same manner as in Example 3, except that a cross-linked polymer was not added as compared with Example 3. Specific components and contents of the surface curing agent according to this comparative example are shown in [Table 1] below.

For the surface curing agent according to each Example and Comparative Example prepared as above, water resistance and acid resistance were evaluated as follows. The results are shown in [Table 1] below.

<Test Example 1>: Water resistance evaluation

A surface curing agent according to each Example and Comparative Example was coated on a glass plate, and then dried to form a coating film. Then, for the coating specimens according to each Example and Comparative Example, water resistance was evaluated through a salt spray test. The salt spray test is performed by spraying salt water on each coating specimen for 30 minutes under the conditions of an aqueous solution of NaCl with a concentration of 10% by weight of brine, a test temperature of 35 ± 0.5 ° C, a spray pressure of 0.098 ± 0.002 MPa, and a spray amount of 1.4 ml/h at 80 cm2. Next, whether discoloration occurred and whether the coating film leaked was visually evaluated. In [Table 1], if there is no discoloration depending on whether or not discoloration occurs, it is expressed as “discoloration” and when discoloration occurs, it is expressed as “discoloration”. If there was runoff, it was indicated as "dissolution".

<Test Example 2>: Acid resistance evaluation

The surface hardening according to each Example and Comparative Example was coated on a glass plate, and then dried to form a coating film. Thereafter, the coating specimens according to Examples and Comparative Examples were immersed in a sulfuric acid aqueous solution (sulfuric acid concentration of 38 wt%) at about 40° C. for 24 hours, and then taken out, and discoloration or pinhole occurrence of each coating film was visually inspected. evaluated. After impregnation in sulfuric acid aqueous solution, if discoloration or pinholes did not occur, “acid resistance”, when discoloration occurred, “discoloration”, and when pinholes occurred, “pinhole” was indicated and shown in [Table 1].

<Composition and characteristic evaluation result of the surface curing agent according to each Example and Comparative Example> note Example 1 Example 2 Example 3 Comparative Example 1 hydrophilic polymer VA-A ⁽¹⁾ 14.0 14.0 - - VA ⁽²⁾ - - 14.0 22.0 crosslinked polymer
(PVA-XG crosslinked product) Synthesis Example 1 [PVA-et-XG ⁽³⁾ ] 8.5 - 8.5 - Synthesis Example 2
[PVA-est-XG ⁽⁴⁾ ] - 8.5 - - Surfactants SBML ⁽⁵⁾ 6.0 6.0 6.0 6.0 moisturizer hyaluronic acid 5.5 5.5 5.5 5.5 glycerin 2.5 2.5 2.5 2.5 dispersant span 80 1.5 1.5 1.5 1.5 water (distilled water) remaining amount remaining amount remaining amount remaining amount Water resistance evaluation No discoloration/waterproof No discoloration/waterproof No discoloration/waterproof discoloration/dissolution Acid resistance evaluation acid resistance discoloration acid resistance discoloration/pinhole
(1) VA-A: vinyl acetate-acrylate copolymer
(2) VA: vinyl acetate copolymer
(3) PVA-et-XG (Synthesis Example 1): polyvinyl alcohol (PVA) and xanthan gum (XG) in alkaline conditions (NaOH)
Etherified derivatives of PVA-XG crosslinked with epichlorohydrin (ECH)
(4) PVA-est-XG (Synthesis Example 2): polyvinyl alcohol (PVA) and xanthan gum (XG) were prepared under acidic conditions (acetic acid)
Esterified derivatives of PVA-XG crosslinked with epichlorohydrin (ECH)
(5) SBML: sorbitan monolaurate

As shown in [Table 1], when comparing Examples 1 to 3 and Comparative Example 1 first, the case in which the cross-linked polymer was added (Examples 1 to 3) compared to the case in which the cross-linked polymer was not added (Comparative Example 1) and improved acid resistance. This means that even in the rainy season or rain (acid rain), it can be usefully applied to yards such as soil or coal.

In addition, comparing Example 1 and Example 2, when an etherified derivative of PVA-XG synthesized under alkaline conditions (PVA-et-XG) (Synthesis Example 1) was used as a crosslinked polymer (Example 1), It was found that the esterified derivative of PVA-XG (PVA-est-XG) (Synthesis Example 2) was used to form a stronger film than (Example 2), and thus had excellent acid resistance.

<Test Example 3>

The surface hardener according to Example 1, which showed the best results in the above Examples, was used as a test specimen, and the scattering dust suppression ability was evaluated as follows. Water was used as a control. As a comparative specimen, as a commercial product, a domestic product made by H company, which contains vinyl acetate copolymer as a main component, was used. The comparative specimen (manufactured by H company in Korea) is a product similar to Comparative Example 1 above. Samples and measurement methods are as follows.

1. Sample

- General: General soil collected from the Rhythm City site in Sangok-dong, Uijeongbu-si, Gyeonggi-do (Uijeongbu Rhythm City soil)

- Mud: Mud collected from the site in Jije-dong, Pyeongtaek-si, Gyeonggi-do (Mud made from Pyeongtaek)

- Sand: Sand collected from the Saemangeum site in Gyehwa-hwa, Buan-gun, Jeollabuk-do (Saemangeum sand)

- Coal: bituminous coal

2. Measurement method

2.1 TSP (high-capacity air entrapment)

Particulate matter in the air is collected on the filter paper by using a high-capacity air sampler at an air flow rate of 1.2 ~ 1.7 ㎥/min. (TSP) is a method of measuring concentration. The filter paper to be used for sampling is stored until it becomes constant weight at a temperature of 20°C and a relative humidity of 50% in advance, and it is an analytical scale with a sensitivity of 0.01 mg or more. was collected on filter paper. After the measurement, the relative humidity was set to 50% again, and the weight was weighed with a microelectronic balance.

2.2 Fine dust (small volume air capture method)

When collecting fine dust (PM10, PM2.5) in the indoor air at an air flow rate of 1 ~ 30 L/min on filter paper, use a particle size separator to separate as much as possible _{PM 10 from the dust, and} This is a method to measure the concentration of fine dust in indoor air using the difference. The filter paper to be used for sampling is stored until it becomes constant weight at a temperature of 20°C and a relative humidity of 50% in advance. As a method of collecting on filter paper using

3. Evaluation of scattering dust suppression ability - Indoor evaluation (1)

First, a test specimen (diluent) in which water was diluted 20 times in a surface curing agent (Example 1) was prepared, and this was sprayed on each sample (about 3.3 kg) in a closed space. Water sprayed was compared as a control. Attached FIG. 2 is a photograph showing a test overview and a view of the test. 3 is a photograph of each sample showing a state that 24 hours have elapsed after spraying the test specimen. After 24 hours of spraying, a strong wind was applied to each sample at a wind speed of 8 m/s for 20 seconds. Then, the concentration was measured by collecting dust from each sample for 60 minutes, and the results are shown in [Table 2] below.

< Results of scattering dust suppression performance - Indoor evaluation (1) > Test Items area sample Test result (ug/Sm3) reduction rate
(%) real specimen
(20-fold dilution of Example 1) control
(water) scattering dust
(TSP) Saemangeum sand 56 17,312 99.68 Pyeongtaek Mud 138 306 54.92 Uijeongbu general soil 90 100 9.83 fine dust
(PM10) Saemangeum sand 348 4,669 92.54 Pyeongtaek Mud 109 179 39.26 Uijeongbu general soil 176 212 17.10

As shown in [Table 1], as a result of the measurement of TSP and PM10, it was found to have a reduction rate (%) of scattering dust of about 99.6 to 9.8% compared to water spray depending on the type of sample. At this time, it is judged that the general soil in Uijeongbu does not show a significant difference in reduction rate (%) due to the large difference in specific gravity because the particle size of the collected soil is large. On the other hand, in the case of the small and light Saemangeum sand, it was found that there was a significant difference in the reduction rate (%) of more than 90%.

4. Evaluation of scattering dust suppression ability - Indoor evaluation (2)

This test was conducted in the same closed space as in the indoor evaluation (1), but a pile of coal was used as a sample. First, a test specimen (diluent) obtained by diluting water 20 times in a surface curing agent (Example 1) was prepared, and this was sprayed on a pile of coal. After 24 hours of spraying, the ability to suppress scattering dust was investigated by radiating strong winds to the coal pile. In addition, the test was conducted on water spray and comparative specimens (20-fold dilution of water from the existing H company).

Coal concentration according to wind speed (0 m/s, 10 m/s, 20 m/s) was measured. At this time, 0.104, the average of the indoor concentration values before and after the test, was used as a control group, and the final concentration value was divided into the control group in each wind speed condition, and then expressed as a percentage for comparison. That is, the scattering dust ratio (%) was evaluated according to the following [Equation 1]. The results are shown graphically in FIG. 4 .

[Equation 1]

In addition, the concentration at the time of water spraying in each wind speed condition was used as a control, and the concentration of each test sample and the comparison sample were substituted to evaluate the reduction efficiency (%) compared to water spraying. That is, the reduction efficiency (%) compared to water injection was evaluated according to the following [Equation 2]. The results are shown graphically in FIG. 5 .

[Equation 2]

As shown in the accompanying FIG. 4, it was found that the dust suppression ability was highly evaluated in all wind speed conditions when the test specimen was applied. In addition, when comparing the reduction efficiency (%) of the experimental specimen and the comparative specimen with water spray as a control, it was found that the working specimen was remarkably superior. That is, as shown in FIG. 5, the comparative specimen (conventional H company product) was 5.74% under the wind speed 0 m/s condition, but the actual sample was 8.2%, and the comparative specimen (conventional H company product) was 8.2% under the 100 m/s condition. 18.7%, but the actual specimen was 27.4%, and at 20 m/s, the comparative specimen (existing product of H Company) was 15.8%, but the actual specimen was 21.5%, indicating that it had excellent reduction efficiency (%) in all wind speed conditions. .

5. Fugitive dust suppression performance evaluation - Field evaluation

An on-site evaluation was conducted to find out the ability to suppress scattering dust generated from external sites. This site evaluation was conducted at our construction sites located in Rhythm City, Uijeongbu, Jije, Pyeongtaek, and Saemangeum. Attached FIG. 6 is a photograph showing a measurement location in each area, and FIG. 7 is a photograph showing a measurement state in each area.

First, a test specimen (diluent) for each magnification in which water was diluted 5 times, 10 times, 20 times and 50 times in the surface curing agent (Example 1) was prepared, and this was sprayed to each area. After spraying, fine dust (PM10, PM2.5) concentrations were measured according to time (date) for each region using a fine dust meter (USB) (model name: DT-9880M/9881M). In addition, water sprinkling was used as a control.

The above field evaluation results are shown in the accompanying FIGS. 8 to 12 . As shown in the accompanying FIGS. 8 to 12, when the test specimen (Example 1) was applied, it was found that the excellent scattering dust (fine dust) suppression ability was maintained even though many days have passed since spraying. In addition, given that it maintains its ability to suppress scattering dust (fine dust) despite wind, rain and snow falling for many days, it was evaluated on-site for its excellent durability, water resistance and wind resistance. could also be checked.

Claims (10)

reacting at least one selected from polyvinyl alcohol and gums with a crosslinking agent to produce a crosslinked polymer crosslinked by at least one selected from polyvinyl alcohol and gums by a crosslinking agent; and
and mixing a hydrophilic polymer, a surfactant, and water with the crosslinked polymer,
The crosslinking agent comprises at least one selected from epichlorohydrin and epibromohydrin,
The reaction is a method for producing a surface curing agent that proceeds under alkaline conditions of pH 9 to 12.
reacting polyvinyl alcohol, a gum, and a crosslinking agent to produce a polyvinyl alcohol-gum crosslinked product in which polyvinyl alcohol and a gum are crosslinked by a crosslinking agent; and
A step of mixing a hydrophilic polymer, a surfactant, and water with the polyvinyl alcohol-gum-based crosslinked product,
The crosslinking agent comprises at least one selected from epichlorohydrin and epibromohydrin,
The reaction is a method for producing a surface curing agent that proceeds under alkaline conditions of pH 9 to 12.
a step of reacting a gum with a crosslinking agent to obtain a gum-crosslinking agent in which a gum and a crosslinking agent are combined;
adding and reacting polyvinyl alcohol to the gum-crosslinking agent to produce a polyvinyl alcohol-gum crosslinked product in which polyvinyl alcohol and gum are crosslinked by a crosslinking agent; and
A step of mixing a hydrophilic polymer, a surfactant, and water with the polyvinyl alcohol-gum-based crosslinked product,
The crosslinking agent comprises at least one selected from epichlorohydrin and epibromohydrin,
The reaction is a method for producing a surface curing agent that proceeds under alkaline conditions of pH 9 to 12.
4. The method according to any one of claims 1 to 3,
The method for producing a surface curing agent wherein the gum is at least one selected from xanthan gum, agar gum, guar gum, tara gum and locust bean gum.
delete delete delete delete delete delete

Images