KR102296828B1 - Powder coating paint composition comprising glass beads - Google Patents

Abstract

The present invention relates to a powder coating paint composition including glass beads. The powder coating paint composition including glass beads according to the present invention includes an acrylic emulsion resin, an epoxy resin, a phosphorus-based monomer, glass beads, ethylene glycol, calcium carbonate, shungite powder, calcined beads, an antifreeze agent, a dispersant, and an isocyanate. The powder coating paint composition including glass beads according to the present invention includes glass beads, so excellent visibility can be secured even at night or in rainy weather, collisions and contact accidents with road structures can be prevented in advance, and there are excellent effects such as a corrosion blocking effect, waterproofness, abrasion resistance, etc.

Description

Powder coating paint composition including glass beads {POWDER COATING PAINT COMPOSITION COMPRISING GLASS BEADS}

The present invention relates to a powder coating paint composition including glass beads, and more particularly, by configuring the powder coating paint composition including glass beads, excellent visibility can be secured even at night or in rainy weather, and collisions and contact accidents with road structures It relates to a powder coating paint composition including glass beads that can prevent contamination in advance and have excellent effects such as corrosion blocking effect, water resistance, and abrasion resistance.

Powder coating is a method of making a synthetic resin powder, coating it on the metal surface, and melting it at a high temperature to finish it. This powder coating has the effect that the coating surface is clean and the coating does not come off or discolor easily for a long time.

Accordingly, in recent years, there have been many cases of powder coating on the surface of a metal, that is, a to-be-coated object.

On the other hand, road structures such as steel, wood, and epoxy installed on the road are corroded by various factors after installation, or the road structures are peeled off or broken by debris generated from a running vehicle, which leads to severe corrosion.

Conventionally, in order to prevent damage to the structure, after coating the iron powder rust-preventive primer such as an epoxy powder rust-preventive primer, the top-coat powder coating or thick coating is applied twice or more to prevent corrosion, and the powder coating is broken by debris from vehicles Efforts have been made to prevent these phenomena.

In particular, the steel used for road structures is severely corroded after installation or the powder coating film is severely broken by debris from running vehicles. Systems intended to prevent corrosion and breakage are widely used.

However, in the case of pre-coating the anti-rust primer for powder iron, the coating time is prolonged and the coating is also performed twice, which can cause a decrease in interlayer adhesion, and is also very uneconomical than a one-time finishing coating. The system in which the top coat powder coating is applied thickly twice also has the same problems as the system in which the rust preventive primer for powder iron material is applied in advance.

And in general, various signs necessary to promote the safety and smooth communication of road traffic are installed in road structures or various facilities installed on road structures, and they supplement safety signs, or provide regulations or instructions to drivers or pedestrians alone. By transmitting the information, it is possible to provide in advance the necessary visual information so that the driver or pedestrian on the road can safely drive the vehicle or walk.

These road structures or various facilities installed in road structures provide linear information and indications of road structures or various facilities installed in road structures to drivers or pedestrians in advance by allowing each visual information to be distinguished not only during the daytime but also at night. should be able to

However, at night, unlike in the daytime, indirect lighting around road structures is small, so it has no choice but to depend only on the amount of light such as car headlights. There was a problem with exposure.

Domestic Registered Patent No. 10-1780896 (Registered on September 15, 2017) Domestic Registered Patent No. 10-1831411 (Registered on February 14, 2018) Domestic Registered Patent No. 10-1546686 (Registered on August 18, 2015)

The present invention can secure excellent visibility even at night or in rainy weather by composing a powder coating paint composition including glass beads, and can prevent collisions and contact accidents with road structures in advance, excellent corrosion blocking effect, waterproofness, abrasion resistance, etc. An object of the present invention is to provide a powder coating paint composition including glass beads having an excellent effect.

Various problems to be solved by the present invention are not limited to the above-mentioned problems, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

The powder coating paint composition including glass beads according to the present invention includes an acrylic emulsion resin, an epoxy resin, a phosphorus-based monomer, glass beads, ethylene glycol, calcium carbonate, pure git powder, calcined beads, an antifreeze agent, a dispersant and an isocyanate.

30 to 40 parts by weight of the acrylic emulsion resin, 10 to 20 parts by weight of an epoxy resin, 5 to 15 parts by weight of a phosphorus monomer, 1 to 10 parts by weight of glass beads, 1 to 5 parts by weight of ethylene glycol, 2 to 6 parts by weight of calcium carbonate, It may be included in a weight ratio of 1 to 2 parts by weight of pure jit powder, 0.5 to 1.5 parts by weight of calcined beads, 0.1 to 0.5 parts by weight of antifreeze agent, 0.3 to 0.7 parts by weight of dispersant, and 0.2 to 0.6 parts by weight of isocyanate.

Specific details of other embodiments are included in the detailed description.

The powder coating paint composition including glass beads according to the present invention can secure excellent visibility even at night or in rainy weather by including glass beads, and can prevent collisions and contact accidents with road structures in advance, and excellent corrosion blocking effect, waterproofness , abrasion resistance, etc. are excellent.

It will be fully understood that embodiments of the technical idea of the present invention may provide various effects not specifically mentioned.

1 is a cross-sectional view schematically showing a state in which a powder coating paint composition including glass beads according to the present invention is coated on the surface of a road structure to form a coating film.
Figure 2 is a photograph showing the night visibility of the steel structure for roads coated with the composition according to Example and Comparative Example 1.

Advantages and features of the present invention, and a method of achieving them, will become apparent with reference to the embodiments described below in detail. However, the present invention is not limited to the embodiments described herein and may be embodied in other forms. Rather, the embodiments introduced herein are provided so that the disclosed subject matter may be thorough and complete, and that the spirit of the present invention may be sufficiently conveyed to those skilled in the art.

The terms used in the present application are only used to describe specific embodiments, and are not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in a commonly used dictionary should be interpreted as having a meaning consistent with the meaning in the context of the related art, and should not be interpreted in an ideal or excessively formal meaning unless explicitly defined in the present application. does not

Hereinafter, a preferred embodiment of the powder coating paint composition including the glass bead according to the present invention will be described in detail with reference to the accompanying drawings.

1 is a cross-sectional view schematically showing a state in which a powder coating paint composition including glass beads according to the present invention is coated on the surface of a road structure to form a coating film.

Referring to FIG. 1 , the powder coating paint composition including glass beads according to the present invention is coated once on road structures 100 such as steel, wood, and epoxy facilities to form a coating film 200, so that even at night or in rainy weather. Excellent visibility of the structure 100 can be secured, thereby preventing collisions and contact accidents with road structures in advance, and the physical properties of the coating film 200 such as corrosion blocking, waterproofing, and abrasion resistance are excellent.

The powder coating paint composition including glass beads according to the present invention includes an acrylic emulsion resin, an epoxy resin, a phosphorus-based monomer, glass beads, ethylene glycol, calcium carbonate, pure git powder, calcined beads, an antifreeze agent, a dispersant and an isocyanate.

In addition, the powder coating paint composition including the glass beads according to the present invention contains 30 to 40 parts by weight of an acrylic emulsion resin, 10 to 20 parts by weight of an epoxy resin, 5 to 15 parts by weight of a phosphorus-based monomer, 1 to 10 parts by weight of glass beads, and ethylene glycol. 1 to 5 parts by weight, 2 to 6 parts by weight of calcium carbonate, 1 to 2 parts by weight of pure jit powder, 0.5 to 1.5 parts by weight of calcined beads, 0.1 to 0.5 parts by weight of antifreeze agent, 0.3 to 0.7 parts by weight of dispersant, and 0.2 to 0.6 part by weight of isocyanate It may be included in a weight ratio of parts by weight.

The acrylic emulsion resin has a low film-forming temperature and excellent flexibility even without the use of a plasticizer, as well as excellent weather resistance and abrasion resistance. The acrylic emulsion resin may be prepared by including 1 to 5 parts by weight of the crosslinking monomer and 0.1 to 1 parts by weight of the stabilizer based on 100 parts by weight of the monomer composition.

The monomer composition includes an alkenyl aromatic monomer; acrylonitrile; alkyl esters, (hetero)cycloalkyl ((hetero)cycloalkyl) esters or aralkyl esters of acrylic acid and methacrylic acid having 4 to 22 carbon atoms; acrylamide and methacrylamide N-substituted with an alkyl, cycloalkyl or aralkyl group having 1 to 18 carbon atoms; vinyl acetate; And one or more monomers selected from the group consisting of vinyl versatate may be used.

The crosslinkable monomer serves to impart a crosslinking function to the acrylic emulsion resin and may enhance adhesion of the acrylic emulsion resin, wherein the crosslinkable monomer is a hydroxy functional monomer, amino Any one selected from the group consisting of a functional monomer, an epoxy functional monomer, a carbonyl functional monomer, and a methyol functional monomer may be used.

The hydroxy functional monomer may be any one or more monomers selected from the group consisting of 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxybutyl acrylate, and the amino functional monomer is N One or more monomers selected from the group consisting of ,N-dimethyl aminoethyl methacrylate, N,N-dimethyl aminoethyl acrylate and N,tert-butyl aminoethyl methacrylate may be used, and the epoxy functional monomer may be glycidyl methacrylate, and the carboxyl The Bonyl functional monomer may be any one or more monomers selected from diacetone acrylamide or acetoacetoxyrthyl metacrylate, and the methylol functional monomer may be any one or more monomers selected from the group consisting of N-methylol acrylamide, N-methylol methacrylamide and Nn-isobutoxymethyl acrylamide. can be used

The stabilizer is added to improve the physical and chemical stability of the acrylic emulsion resin, and the stabilizer may be any one selected from allyl alkyl sulfonate or copolymerizable sulfonate monomer.

In the present invention, 30 to 40 parts by weight of the acrylic emulsion resin may be included in the total content of the paint composition. When the acrylic emulsion resin is included in less than 30 parts by weight, the hardness of the coating film 200 coated on the road structure 100 Adjustment or gloss and smoothness are difficult to be sufficiently imparted, and when more than 40 parts by weight is included, components of other compositions are relatively reduced and the overall physical properties of the road structure 100 are not balanced, so the overall physical properties of the coating film 200 are may be lowered.

The epoxy resin is a kind of thermosetting plastic and has excellent adhesion. The epoxy resin is a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a brominated epoxy resin, a hydrogenated bisphenol-A type epoxy resin, a Novolac epoxy resin, a Phenol epoxy resin, and other two or more epoxy groups in the molecule It is possible to use an epoxy resin having a bisphenol (Bisphenol) A type epoxy resin may be used.

The bisphenol A type epoxy resin may be a mixture of a bisphenol A type epoxy resin having an epoxy equivalent of 185 to 190 and a bisphenol A type epoxy resin having an epoxy equivalent of 500 to 600 in a 1:1 weight ratio.

10 to 20 parts by weight of the epoxy resin may be included in the total content of the paint composition. When the epoxy resin is included in less than 10 parts by weight, it may be difficult to provide sufficient adhesion, and it may be included in excess of 20 parts by weight. In this case, adhesiveness is increased, but the amount of other additives is relatively decreased, which may cause a problem of reducing workability and durability.

The phosphorus-based monomer may be used to improve adhesion to a road structure to which the powder coating paint composition including the glass beads according to the present invention is applied and to improve rust prevention properties of road structures, particularly metal. Any one or more selected from phosphate (Mono alkyl phosphate) or dialkyl phosphate (Di alkyl phosphate) may be used.

Specifically, for example, as the phosphorus-based monomer, bis[2-(methacryloxy)ethyl]phosphate (Bis[2-(methacyloyloxy)ethyl] phosphate, DMEP), 2-(methacryloxy)ethyl phosphate (2- At least one selected from the group consisting of (methacryloyloxy) ethyl phosphate, MMEP) and tris 2-(methacryloyloxy)ethyl phosphate (TMEP) may be included.

The glass bead may be included in the powder coating paint composition to ensure excellent visibility even at night or in rainy weather, thereby preventing an accident in which a driver or pedestrian collides or comes into contact with a road structure in advance.

As the glass beads, glass beads prepared by mixing various additives by the following method may be used.

In order to prepare the glass beads, first, a mixed resin solution containing an epoxy resin may be prepared.

In the above step, the epoxy mixed resin solution may act as a binder for mixing and bonding pigments, photoluminescent pigments, processed glass, etc. in a later process. The epoxy mixed resin solution is a self-emulsifying epoxy resin, acrylic modified polyester resin and poly It can be prepared by mixing vinyl alcohol.

Specifically, the epoxy mixed resin solution may be prepared by mixing 20 to 30 parts by weight of a self-emulsifying epoxy resin, 10 to 20 parts by weight of an acrylic-modified polyester resin, and 5 to 15 parts by weight of polyvinyl alcohol.

The self-emulsifying epoxy resin is an epoxy resin having an active group that can be emulsified in itself, and the self-emulsifying epoxy resin is a self-emulsifying modified epoxy resin having an epoxy equivalent of 200 to 220 g/eq. , water resistance, etc. can be remarkably improved.

20 to 30 parts by weight of the self-emulsifying epoxy resin is used, but when the self-emulsifying epoxy resin is included in an amount of less than 20 parts by weight, physical properties such as sufficient strength, weather resistance, and water resistance cannot be obtained, and more than 30 parts by weight When included, a problem of delayed drying may occur.

The acrylic-modified polyester resin is a hydroxyl group by condensation polymerization of a polyhydric alcohol containing 80 to 90% by weight of a diol and 10 to 20% by weight of a triol with a polybasic acid containing 40 to 50% by weight of anhydrous acid and 50 to 60% by weight of an aliphatic acid A polyester resin having a value of 45 to 65 mgKOH / g, an acid value of 3 mgKOH / g or less, a glass transition temperature of 5 to 20 ° C. and a weight average molecular weight (Mw) of 2,500 to 3,500 is prepared, and the polyester resin is 50 to 60 weight % and 40 to 50 wt% of an acrylic monomer are grafted to have a weight average molecular weight (Mw) of 5,000 to 7,000, a hydroxyl value of 50 to 60 mgKOH/g, an acid value of 3 mgKOH/g or less, and a glass transition temperature of 10 to 20 ° C. It is possible to prepare an acrylic-modified polyester resin in the range.

The polyvinyl alcohol is an eco-friendly material, has the advantage of imparting emulsification, water-resistance, and viscosity stability, has good compatibility with the resin, and may be suitable for viscosity control when manufacturing luminous accessories. In the present invention, polyvinyl alcohol having a molecular weight of 20,000 to 80,000 may be used as the polyvinyl alcohol.

Next, a pigment, a photoluminescent pigment, and a processed glass may be mixed with the epoxy mixed resin solution.

In the above step, it is possible to implement various colors including the pigment, and to improve the reflectivity and visibility of light by including a photoluminescent pigment and processed glass, and the pigment is used to sufficiently represent the required color, Copper, manganese, cobalt, chromium, nickel, zinc, calcium and a metal oxide containing any one component selected from silver, complex oxide, metal sulfide or metal carbonate, carbon black, titanium black and selected from the group consisting of titanium dioxide Any one or more pigments may be used.

The photoluminescent pigment may be included to ensure excellent visibility even at night or in rainy weather, and the photoluminescent pigment includes europinium (Eu), gadolinium (Gd), dysprosium (Dy), terbium (Tb) and ytterbium (Yb). ), an inorganic phosphorescent pigment that is a composite of an alumina component of an alkaline earth metal doped with any one or more rare earth elements selected from the group consisting of A complex of any one or more salts selected from the group consisting of magnesium oxide may be used.

For example, the photoluminescent pigment is Al ₂ O ₃ CaO 3 to 5 parts by weight, Al ₂ O ₃ MgO 2 to 4 parts by weight, SrAl ₂ O ₄ 1 to 3 parts by weight, and Al ₂ O ₃ CaOSrOB ₂ O ₃ 2 to A complex of salts mixed in a weight ratio of 4 parts by weight may be used, and the photoluminescent pigment may preferably have an average particle diameter of 10 to 200 nm.

The processed glass is high-strength glass reprocessed by heating the waste glass, and the particle diameter may be 10 to 100 nm. For example, the processed glass is melted by grinding the waste glass and then heated at a temperature of 600 to 700 ° C. The molten waste glass is frozen at a temperature of -30 to -40° C. to prepare a primary processed waste glass, and the primary processed waste glass is pulverized once again and then melted by heating at a temperature of 600 to 700° C. The molten waste glass may be manufactured through a process of secondary freezing at a temperature of -20 to -30°C.

In this case, the processed glass may be processed in the form of a glass grain so that there is no sharp part, and the processed glass formed in the form of the glass may reflect light even in small indirect lighting around the road structure to improve visibility of a driver or a pedestrian.

In the above step, 2 to 4 parts by weight of the pigment, 1 to 5 parts by weight of the photoluminescent pigment, and 3 to 5 parts by weight of the processed glass may be mixed in the epoxy mixed resin solution.

Next, after mixing the curing agent in the epoxy mixed resin solution in which the pigment, the photoluminescent pigment and the processed glass are mixed, it is put into a mold and semi-cured to prepare a molded prototype.

In the above step, the curing agent is mixed with the epoxy mixed resin solution in which the dye, the photoluminescent pigment and the processed glass are mixed, and then put into a mold and semi-cured to prepare a molded prototype, wherein the mold has a certain shape, for example, It may be a mold that conforms to the shape of a rectangular parallelepiped.

In addition, in the above step, 1 to 3 parts by weight of a curing agent is mixed with the epoxy mixed resin solution in which the dye, the photoluminescent pigment and the processed glass are mixed, and then maintained at a temperature of 50 to 60° C. for 30 to 60 minutes, the epoxy mixed resin solution It is possible to manufacture a molded prototype in a semi-hardened state having fluidity, not in a completely hardened state.

The curing agent is included in the epoxy mixed resin solution in which the dye, the photoluminescent pigment and the processed glass are mixed to perform a curing function, and as the curing agent, a curing agent resin and a curing accelerator may be mixed and used.

Modified aliphatic polyamine may be used as the curing agent resin, and 2,4,6-tridimethylaminomethyl phenol may be used as the curing accelerator, and the curing agent resin and the curing accelerator are each 10 to 20 parts by weight of the curing agent resin. and 5 to 10 parts by weight of the curing accelerator may be mixed and prepared.

Then, the molded article can be prepared by heating and baking the semi-hardened molded article.

In the above step, the molded article can be prepared by heating and baking the semi-hardened molded prototype at a temperature of 180 to 200° C. for 5 to 10 minutes. In this step, the semi-hardened molded prototype is heated and baked at a high temperature. By manufacturing the molding, it is possible to prevent the manufactured glass beads from being easily worn or deformed by external impact or changes in temperature, humidity, and the like.

Next, a pulverized glass product may be prepared by pulverizing the molded product.

In the above step, a pulverized glass product having a small particle size can be manufactured by pulverizing the molded product using a known pulverizer. The configuration of pulverizing using the pulverizer is a known technique, so convenience of explanation and clarity of the technical idea of the present invention For this purpose, a detailed description thereof will be omitted.

Next, a coating solution is applied to the surface of the pulverized glass and dried to prepare glass beads.

In the above step, it is possible to improve scratch resistance and improve the strength of the glass bead surface by applying a coating solution to the surface of the crushed glass material and then drying it. After coating on the surface of the crushed glass, it can be prepared by curing with a UV lamp with an irradiation amount of ^{300 to 350 mJ/cm 2 in a UV coating device.}

The UV curable coating solution may be prepared by mixing a urethane acrylate oligomer, a filler, and a photoinitiator in a predetermined weight ratio. It may be prepared by mixing in a weight ratio of 1.5 parts by weight.

The urethane acrylate oligomer is UV-curable, and 20 to 30 parts by weight may be included in the total content of the UV-curable coating composition. When included in excess of parts by weight, it may be difficult to control the viscosity of the coating solution.

The filler affects thermal and physical strength improvement, wear prevention and tearing of the manufactured glass bead, and is added to improve corrosion resistance, weather resistance and gloss. For example, the filler includes perlite, vermiculite (Vermiculite), barite (Barite), talc (Talc), diatomaceous earth (diatomaceous earth), graphite (Graphite), silica, calcium carbonate, magnesium silicate, calcium silicate, zinc phosphate and any one or more selected from the group consisting of barium sulfate It is preferably used and has an average particle diameter of 10 to 100 nm.

The photoinitiator may be used for polymerization by activating radicals generated by UV. As the photoinitiator, a known UV photoinitiator may be used. For example, as the photoinitiator, benzophenone (BP), benzylke Any one or more selected from the group consisting of de-based (IC-651, BDK) and acetophenone-based (IC-184, HP-8) may be used.

The ethylene glycol may be added to improve fluidity and workability before curing, and to improve physical and chemical performance after curing.

The ethylene glycol may be included in 1 to 5 parts by weight in the total content of the paint composition, but when the ethylene glycol is included in less than 1 part by weight, there may be a problem that the effect of adding the ethylene glycol is not sufficiently exhibited, 5 When it is included in excess of parts by weight, the overall physical properties of the coating film 200 for the road structure 100 to be manufactured may be deteriorated.

The calcium carbonate (Calcium Carbonate) is used as an inorganic filler included in the paint composition, increases the initial adhesion by increasing the apparent viscosity, reduces shrinkage and expansion during curing to improve workability and adhesion, and heat resistance and durability of the paint composition can play a role in improving it.

The calcium carbonate (Calcium Carbonate) has the most chemical formula CaCO ₃ among salts that exist in nature, and has various forms, such as marble, calcite, berne, limestone, chalk, ice tin (氷洲石), seashell, eggshell, Coral, etc. may exist. The calcium carbonate is generally colorless crystals or white solid, has a specific gravity of 2.93, can be decomposed at 825° C., and when heated _{to generate carbon dioxide (CO 2} ) and obtain quicklime (CaCO3 → CaO + CO2 ↑) .

The calcium carbonate is inexpensive and does not have a large specific gravity, so it can be widely used in industrial fields. The calcium carbonate is limestone marble, which can be used as a main raw material for cement, a raw material for calcium oxide, and as a neutralizing agent for building materials. Wheat flour is used for white pigments and water-based paints, and precipitated calcium carbonate is used for pigments, paints, toothpaste, etc., and can also be formulated as a reinforcing agent in rubber.

The calcium carbonate has a particle size of 0.1 to 10 μm, and 2 to 6 parts by weight may be included in the total content of the paint composition. , the expansion effect may be insignificant, and if it is included in excess of 6 parts by weight, the physical properties of the paint composition may be deteriorated and workability and adhesion may be deteriorated.

The pure jit powder may be manufactured by pulverizing and pulverizing pure jit minerals, and the shungite _{is a material containing SiO 2} (silicate) and C ₆₀ (fullerene) as main components, and a material containing natural fullerene. means Pure shungite containing more than 90% fullerene is called elite shungite or noble shungite, and pure shungite containing less than 60% fullerene is called normal shungite.

The representative function of the Sunjit is an antioxidant function, an electromagnetic wave blocking function, a purification and decomposition function of contaminants, and a sterilization and antibacterial function. Sunjit is a powerful natural antioxidant that enhances human immunity against numerous diseases, purifies water and air by adsorbing pollutants, and has the ability to self-decompose adsorbed pollutants.

In addition, since the Sunjit has antibacterial and sterilizing properties, it has a function of removing more than 99% of only E. coli, Pseudomonas aeruginosa, Staphylococcus aureus and harmful bacteria, and has a function of blocking harmful electromagnetic waves and emitting a large amount of far-infrared rays.

1 to 2 parts by weight of the pure git powder may be included in the total content of the paint composition. When the pure git powder is included in an amount of less than 1 part by weight, the effect is insignificant, and when it is included in more than 2 parts by weight, it is manufactured A problem in which the strength of the coating film 200 of the road structure 100 to be used is lowered may occur.

In addition, the pure jite powder may be used pure jite powder prepared by the following method.

First, the pure jite mineral may be prepared and washed to remove foreign substances attached to the pure jite mineral.

The cleaning of the pure jite mineral may be performed by washing the surface of the pure jite mineral using purified water, thereby removing foreign substances remaining on the surface of the pure jite mineral.

Next, the washed pure jit mineral may be first pulverized to prepare a pulverized pure jit granulated product.

In the above step, by first pulverizing the washed pure jite mineral using a granulator, impurities or organic residues of the pure jite mineral can be removed in a later process, and the first pulverization is performed using a granulator. , may be performed using a known granulator such as a drum granulator or a compression pelletizer, but is not necessarily limited to the granulator described above.

Next, the powdered raw material may be immersed in the mixed solution.

In the above step, impurities or organic residues contained in the coarsely granulated and pulverized pure jite may be removed by immersing the pulverized pure jite in the mixed solution. to 1.0 wt%, persulfate 0.01 to 0.05 wt%, acetic acid 1 to 3 wt%, and the remaining amount of purified water, and may be carried out by immersing the pulverized Sunjit granulated product in the mixed solution for 20 to 40 minutes.

In addition, in the above step, the phosphate compound includes sodium phosphate monobasic (NaH ₂ PO ₄ ), sodium phosphate dibasic (Na ₂ HPO ₄ ), sodium phosphate tribasic (Na ₃ PO ₄ ), potassium phosphate first (KH _{2 )} PO ₄ ), potassium phosphate dibasic (K ₂ HPO ₄ ), ammonium phosphate monobasic ((NH ₄ )H ₂ PO ₄ ), ammonium phosphate dibasic ((NH ₄ ) ₂ HPO ₄ ), and ammonium tertiary phosphate (( Any one or more selected from the group consisting of NH ₄ ) ₃ PO ₄ ) may be used, and as the persulfate, ammonium persulfate ((NH ₄ ) ₂ S ₂ O ₈ ), sodium persulfate (Na ₂ S ₂ O _{8 )} ) or potassium persulfate (K ₂ O ₈ S ₂ ) Any one or more selected from may be used.

Subsequently, after separating and taking out the granulated and pulverized pure jite from the mixed solution, the pulverized pulverized pure jite may be heated and calcined using a kiln.

In the above step, by heating the separated pure Jit granulated and pulverized product using a kiln, it is possible to remove and activate contaminants adsorbed in the fine pores of the Sun Jit granulated pulverized product. After being put into the kiln, it can be carried out by heating at a temperature of 1,100 to 1,300 ℃ for 50 to 100 minutes.

Next, a second pulverization of the calcined pure jit granulated pulverized product may be performed to prepare a pulverized pulverized pure jite.

In the above step, it can be carried out by pulverizing the calcined pure jit granulated product using a ball mill or various known pulverizers. can

Next, impurities may be removed from the pulverized pure jit and sterilized to prepare pure git powder.

In the above step, impurities such as heavy metals that may remain in the pulverized pure jit can be removed by rotating the pulverized pure jit in a rotating tub installed with a magnet. It is possible to remove impurities such as heavy metals, which may be included in the Sunjit fine pulverized product, by rotating it for 10 to 20 minutes at a rotation speed of 500 to 1000 RPM after being put into the installed rotary tube.

The firing bead is used to strengthen the physical properties of the coating film 200 formed by coating on the road structure 100, and 0.5 to 1.5 parts by weight of the firing bead may be included in the total content of the paint composition, wherein the firing bead is 0.5 parts by weight When it is included in less than, the expression of the effect is insignificant, and when it is included in excess of 1.5 parts by weight, there may be a problem in that the strength of the coating film 200 of the road structure 100 to be manufactured is lowered.

In addition, the calcined bead may be a calcined bead prepared by the following method.

First, in order to prepare the firing bead, unburned carbon powder, bottom ash, loess and dredged soil are prepared, and water can be prepared as a binder for molding the unburned carbon powder, bottom ash, loess and dredged soil into a predetermined shape. At this time, the loess and dredged soil may be used to improve the caking properties of unburned carbon powder and bottom ash.

In addition, the unburned carbon powder, bottom ash, loess and dredged soil are each mixed in a weight ratio of 5 to 10 parts by weight of unburned carbon powder, 3 to 7 parts by weight of bottom ash, 2 to 4 parts by weight of loess and 1 to 2 parts by weight of dredged soil, and the Water may be mixed in a weight ratio of 30 to 40 parts by weight based on 100 parts by weight of the total unburned carbon powder, bottom ash, loess and dredged soil.

Next, after preparing a mixture by mixing the unburned carbon powder, bottom ash, loess and dredged soil with water, the mixture may be molded into a predetermined shape to form a molded body.

That is, the molded body is mixed in a weight ratio of 5 to 10 parts by weight of unburned carbon powder, 3 to 7 parts by weight of bottom ash, 2 to 4 parts by weight of loess and 1 to 2 parts by weight of dredged soil, and the unburned carbon powder, bottom ash, loess and dredged soil. After preparing a mixture by mixing in a weight ratio of 30 to 40 parts by weight of water with respect to 100 parts by weight of the total, a molded article can be prepared by molding the mixture into various shapes such as a spherical shape and a pellet shape.

Next, the molded body may be heated and fired.

The firing of the molded body may be fired by heating the molded body in a kiln, for example, a tunnel kiln or a discontinuous kiln may be used as the kiln, and the kiln has an internal temperature of 380 to 420° C. It can be maintained at a temperature of, and then fired in an oxidizing or reducing (neutral) atmosphere for 10 to 20 hours while gradually raising the temperature to 1000 to 1100° C. after putting the molded body inside the kiln.

In the above step, the molded body can be put in after maintaining the internal temperature of the kiln at 380 to 420 ° C. can

In addition, after inserting the molded body, it is calcined in an oxidizing or reducing (neutral) atmosphere for 10 to 20 hours while gradually raising the temperature to 1000 to 1100 ° C. When calcined under the same temperature and time conditions as above, the absorption rate is lowered And there may be a problem that it is difficult to manufacture a fired bead of a desired compressive strength, and when the fired bead is fired in excess of the above temperature and time conditions, the effect of improving the properties of the fired bead is insignificant, whereas the cost of high-temperature treatment is rather increased. This may lead to an increase in production cost.

Then, the fired molded body may be cooled to prepare a fired bead.

Cooling of the fired molded body in the above step can be cooled for 2 to 4 hours at a temperature of 200 to 250 ℃ after taking out the molded body from the kiln, and then cooled for 5 to 10 hours at a temperature of 40 to 60 ℃, By cooling the fired molded body through the two-step cooling process as described above, it is possible to prevent surface cracking and a decrease in compressive strength of the fired molded body due to rapid cooling.

The anti-freeze agent is used to impart anti-freeze properties, and the anti-freeze agent may be included in an amount of 0.1 to 0.5 parts by weight based on the total content of the paint composition.

A mixture of calcium nitrate and calcium nitrite may be used as the antifreeze agent, and the antifreeze agent may be prepared by mixing in a weight ratio of 5 to 10 parts by weight of calcium nitrate and 3 to 7 parts by weight of calcium nitrite.

The dispersant may be used to prevent precipitation of the paint composition and to have dispersion properties, and the dispersant may be included in an amount of 0.3 to 0.7 parts by weight based on the total content of the paint composition.

For example, the dispersant is selected from the group consisting of polyester polydimethylsiloxane copolymer, dimethylol butanoic acid (DMBA), dimethylol propionic acid (DMPA), methylenediethanolamine and polyethylene oxide derivatives. Any one or more may be used.

The isocyanate may function as a curing agent, and 1 to 3 parts by weight of the isocyanate may be included in the total content of the paint composition.

For example, the isocyanate (isocyanate) is hexamethylene diisocyanate (Hexamethylene Diisocyanate, HDI), hexamethylene diisocyanate trimer (HDT), isophorone diisocyanate (Isophorone Diisocyanate, IPDI) and cyclohexylmethane diisocyanate (Cyclohexylmethanediisocyanate) H12MDI), one or more isocyanates may be used. Preferably, hexamethylene diisocyanate (HDI) may be used as the isocyanate.

Hereinafter, examples of the powder coating paint composition including the glass beads according to the present invention will be described in more detail.

<Example>

35 parts by weight of acrylic emulsion resin, 15 parts by weight of epoxy resin, 10 parts by weight of phosphorus-based monomer, 5 parts by weight of glass beads, 3 parts by weight of ethylene glycol, 4 parts by weight of calcium carbonate, 1.5 parts by weight of pure git powder, 1 part by weight of calcined beads, After mixing in a weight ratio of 0.3 parts by weight of the antifreeze agent, 0.5 parts by weight of the dispersant, and 0.4 parts by weight of the isocyanate, it was coated on the surface of the steel structure for road use to form a coating film.

< Comparative Example 1 >

A coating film was formed using the same composition as in Example, but in Comparative Example 1, a coating film was formed without including phosphorus-based monomers, glass bis, and fired beads.

< Comparative Example 2 >

A coating film was formed using the same composition as in Example, but in Comparative Example 2, a coating film was formed without including epoxy resin, glass beads, and pure jite powder.

The following test examples are experimental results comparing the characteristics of the Examples according to the present invention and Comparative Examples 1 and 2 in order to more easily grasp the characteristics of the Examples according to the present invention.

<Test Example 1>

After forming a coating film on the surface of the steel structure for road use as in the methods of Examples and Comparative Examples 1 and 2, stability, surface hardness, waterproofness, adhesion, and peelability in the standard state were measured, and the measurement results are shown in [ Table 1].

division Example Comparative Example 1 Comparative Example 2 Stability (kg/f) 1341 952 966 surface hardness no problem weakness weakness Waterproof (%) 99% 83% 84% adherence good middle bad peelability unpeeled slight peeling slight peeling

As shown in [Table 1], when a coating film is formed on the surface of a steel structure using the composition according to the example, it can be confirmed that not only waterproof and adhesive properties are good, but also it is not easily peeled off from the surface and has excellent stability. could

<Test Example 2>

(1) Surface hardness evaluation

Pencil hardness was measured according to KS D 6711.

(2) Water resistance evaluation

The time for continuous surface deformation (cracks, blisters, etc.) to occur in hot water at 90°C was measured.

The evaluation results are shown in [Table 2].

division Example Comparative Example 1 Comparative Example 2 surface hardness 4H 3H 3H water resistance 712hr 454hr 448hr

As shown in [Table 2] above, when a coating film was formed on the surface of the steel structure using the composition according to the example, it was confirmed that the surface hardness and water resistance were remarkably superior to those of Comparative Examples 1 and 2. Accordingly, it was confirmed that, when a coating film was formed on the surface of the steel structure using the composition according to the embodiment, rust prevention and durability could also be improved.

<Test Example 3>

After the paint compositions according to Examples and Comparative Example 1 were applied to the surface of the steel structure for roads, visibility at night was observed.

A traffic sign was used as the steel structure for the road.

Figure 2 is a photograph showing the night visibility of the steel structure for roads coated with the composition according to Example and Comparative Example 1.

Referring to FIG. 2 , it can be seen that the night visibility of the steel structure for roads coated with the composition according to the example is superior to that of the composition according to the comparative example.

In the above, a preferred embodiment of the present invention has been described, but those skilled in the art to which the present invention pertains will understand that the present invention may be embodied in other specific forms without changing the technical spirit or essential features thereof. will be able Therefore, it should be understood that the embodiment described above is illustrative in all respects and not restrictive.

100; road structure
200; film

Claims (2)

30 to 40 parts by weight of acrylic emulsion resin, 10 to 20 parts by weight of epoxy resin, 5 to 15 parts by weight of phosphorus monomer, 1 to 10 parts by weight of glass beads, 1 to 5 parts by weight of ethylene glycol, 2 to 6 parts by weight of calcium carbonate, pure paper 1 to 2 parts by weight of the powder, 0.5 to 1.5 parts by weight of the calcined beads, 0.1 to 0.5 parts by weight of the antifreeze agent, 0.3 to 0.7 parts by weight of the dispersant, and 0.2 to 0.6 parts by weight of the isocyanate,
The epoxy resin is a mixture of a bisphenol A type epoxy resin having an epoxy equivalent of 185 to 190 and a bisphenol A type epoxy resin having an epoxy equivalent of 500 to 600 in a 1:1 weight ratio,
The glass beads prepare an epoxy mixed resin solution, wherein the epoxy mixed resin solution contains 20 to 30 parts by weight of a self-emulsifying epoxy resin, 10 to 20 parts by weight of an acrylic-modified polyester resin, and 5 to 15 parts by weight of polyvinyl alcohol. and then mixing, and the self-emulsifying epoxy resin uses a self-emulsifying modified epoxy resin having an epoxy equivalent of 200 to 220 g/eq, and the acrylic modified polyester resin contains 80 to 90 wt% of diol and 10 triol By condensation polymerization of a polyhydric alcohol containing ~20% by weight with a polybasic acid containing 40 to 50% by weight of anhydrous acid and 50 to 60% by weight of an aliphatic acid, the hydroxyl value is 45 to 65 mgKOH/g, the acid value is 3 mgKOH/g or less, glass transition A polyester resin having a temperature of 5 to 20° C. and a weight average molecular weight (Mw) of 2,500 to 3,500 is prepared, and 50 to 60% by weight of the polyester resin and 40 to 50% by weight of an acrylic monomer are grafted. An acrylic-modified polyester resin having a weight average molecular weight (Mw) of 5,000 to 7,000, a hydroxyl value of 50 to 60 mgKOH/g, an acid value of 3 mgKOH/g or less, and a glass transition temperature in the range of 10 to 20° C. is used, and the epoxy mixed resin solution 2 to 4 parts by weight of the pigment, 1 to 5 parts by weight of the photoluminescent pigment, and 3 to 5 parts by weight of the processed glass, but the pigment is any one selected from iron, copper, manganese, cobalt, chromium, nickel, zinc, calcium and silver one or more pigments are used, and the phosphorescent pigment is selected from metal oxides, composite oxides, the group consisting of a metal sulfide or a metal carbonate, carbon black, titanium black and titanium dioxide containing a component of the Al ₂ O ₃ CaO ₃ to 5 A complex of salts mixed in a weight ratio of 2 to 4 parts by weight, Al ₂ O ₃ MgO 2 to 4 parts by weight, SrAl ₂ O ₄ 1 to 3 parts by weight, and Al ₂ O ₃ CaOSrOB ₂ O _{3 2 to 4 parts by weight, is used, and the phosphorescence} The pigment has an average particle diameter of 10 to 200 nm, and the processed glass divides waste glass. After crushing, it is melted by heating at a temperature of 600 to 700 ° C., and then the molten waste glass is frozen at a temperature of -30 to -40 ° C. to prepare a primary processed waste glass, and the primary processed waste glass is once again Processed glass having a particle diameter of 10 to 100 nm is used, which is produced through a process of grinding and melting by heating at a temperature of 600 to 700 ° C. and secondary freezing of the molten waste glass at a temperature of -20 to -30 ° C., After mixing 1 to 3 parts by weight of a curing agent in the epoxy mixed resin solution in which the pigment, photoluminescent pigment and processed glass are mixed, the mixture is maintained at a temperature of 50 to 60° C. for 30 to 60 minutes to prepare a semi-cured molded prototype, As the curing agent, a curing agent resin and a curing accelerator are mixed, the curing agent resin is a modified aliphatic polyamine, the curing accelerator is 2,4,6-tridimethylaminomethyl phenol, and the curing agent resin and the curing accelerator are used. is used in a mixture in a weight ratio of 10 to 20 parts by weight of the curing agent resin and 5 to 10 parts by weight of the curing accelerator, respectively, and the semi-hardened molded product is heated and baked at a temperature of 180 to 200° C. for 5 to 10 minutes. is prepared by manufacturing, pulverizing the molded product to prepare a pulverized glass product, applying a coating solution to the surface of the pulverized glass product, and then drying, the coating solution is a UV curable coating solution, and the UV curable coating solution is It is prepared by applying to the surface of the glass pulverized product ^{and curing it with a UV lamp with an irradiation amount of 300 to 350 mJ/cm 2} in a UV coating device, and the UV curable coating solution is 20 to 30 parts by weight of a urethane acrylate oligomer, 1 to 1 filler It is prepared by mixing 3 parts by weight and 0.5 to 1.5 parts by weight of the photoinitiator, and the filler is Perlite, Vermiculite, Barite, Talc, diatomaceous earth, Graphite ), silica, calcium carbonate, magnesium silicate, calcium silica Any one or more selected from the group consisting of Kate, zinc phosphate and barium sulfate is used, and the average particle diameter is 10 to 100 nm,
The pure jit powder is washed after preparing the pure jit mineral, and the washed pure git mineral is first pulverized to prepare a pure git granulated product, and the pure git granulated product is immersed in a mixed solution, the mixture is 0.2 to 0.4% by weight of nitric acid, 0.5 to 1.0% by weight of a phosphate compound, 0.01 to 0.05% by weight of persulfate, 1 to 3% by weight of acetic acid, and the remaining amount of purified water, It is carried out by immersion in the mixed solution, and the phosphate compound is sodium phosphate monobasic (NaH ₂ PO ₄ ), sodium phosphate dibasic (Na ₂ HPO ₄ ), sodium phosphate tribasic (Na ₃ PO ₄ ), potassium phosphate first (KH) ₂ PO ₄ ), potassium phosphate dibasic (K ₂ HPO ₄ ), ammonium phosphate monobasic ((NH ₄ )H ₂ PO ₄ ), ammonium phosphate dibasic ((NH ₄ ) ₂ HPO ₄ ) and ammonium tertiary ( Any one or more selected from the group consisting of (NH ₄ ) ₃ PO ₄ ) is used, and the persulfate is ammonium persulfate ((NH ₄ ) ₂ S ₂ O ₈ ), sodium persulfate (Na ₂ S ₂ O ₈ ) Or potassium persulfate (K ₂ O ₈ S ₂ ) At least one selected from is used, and after separating and taking out the granulated Sunjit granulated product from the mixed solution, the Sunjit granulated and pulverized product is put into a kiln, and then 1,100 to 1,300° C. Firing by heating for 50 to 100 minutes at a temperature of Manufactured through a process of removal and sterilization,
The firing bead prepares unburned carbon powder, bottom ash, loess and dredged soil, and prepares water as a binder for molding the unburned carbon powder, bottom ash, loess and dredged soil into a certain shape, the unburned carbon powder, bottom ash, loess And dredged soil is mixed in a weight ratio of 5 to 10 parts by weight of unburned carbon powder, 3 to 7 parts by weight of bottom ash, 2 to 4 parts by weight of loess, and 1 to 2 parts by weight of dredged soil, respectively, and the water is the unburned carbon powder, bottom ash, loess and 30 to 40 parts by weight based on 100 parts by weight of the total dredged soil, and 30 to 40 parts by weight of water based on 100 parts by weight of the unburned carbon powder, bottom ash, loess and dredged soil to prepare a mixture Then, the mixture is molded to form a molded body, and the molded body is heated and fired in a kiln, but the kiln maintains the internal temperature at a temperature of 380 to 420 ° C., and after putting the molded body inside the kiln 1000 Firing for 10 to 20 hours while raising the temperature to 1100 ° C. After taking out the fired molded body from the kiln, cooling at a temperature of 200 to 250 ° C. for 2 to 4 hours, and then 5 to at a temperature of 40 to 60 ° C. A powder coating paint composition comprising glass beads, characterized in that it was prepared through a process of cooling for 10 hours. delete

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