KR102626073B1 - Composition of eco-friendly hybrid ceramic coating agent with excellent corrosion resistance and acid resistance and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a hybrid ceramic coating and a method for manufacturing the same, and more specifically, to a hybrid ceramic coating with excellent miscibility that can be used in steel and concrete structures, and a method for manufacturing the same.
The eco-friendly hybrid ceramic coating according to the present invention
It includes a main ingredient and a curing agent ingredient, wherein the main ingredient is 30 to 50 parts by weight of an oil-based resin imparted with a polar group, 11 to 16 parts by weight of a coloring pigment, and 8 to 8 to 8 parts by weight of a plate-shaped organic or inorganic material, based on 100 parts by weight of the total main ingredients. It contains 12 parts by weight, 6 to 9 parts by weight of zinc phosphate, 12 to 25 parts by weight of ceramic powder, 3 to 6 parts by weight of additives, and 8 to 12 parts by weight of fresh water, and the curing agent component is water-soluble relative to 100 parts by weight of the total curing agent component. It is characterized in that it contains 75 to 90 parts by weight of an epoxy curing agent, 2 to 5 parts by weight of a curing accelerator, and 10 to 25 parts by weight of fresh water.

Description

Composition of eco-friendly hybrid ceramic coating agent with excellent corrosion resistance and acid resistance and manufacturing method thereof}

The present invention relates to a hybrid ceramic coating and a manufacturing method thereof, and more specifically, to an eco-friendly hybrid ceramic coating with excellent miscibility that can be used in steel and concrete structures, etc., and a manufacturing method thereof.

There are many reasons why the durability of various structures, such as steel structures or concrete structures, decreases. Since the durability of most structures decreases over time, the durability lifespan must be taken into consideration when designing the structure. However, due to causes such as design that does not consider the external environment, poor construction, poor concrete placement, freezing and thawing during the winter, and especially external corrosion and deterioration factors, the durability life is shortened due to rapid corrosion in the case of steel structures, and in the case of concrete structures, Corrosion of reinforcing bars due to neutralization, cracking and falling off due to salt damage and freezing and thawing occur, drastically shortening the durability of the structure. Accordingly, the durability of the structure is secured through various methods, but despite these efforts, it is difficult to secure the durability of the initially designed structure due to various factors.

In particular, in the case of Korea, there is a clear change in climate across the four seasons, and as it is surrounded by the sea on three sides, structural corrosion and corrosion are caused by external environments such as frequent acid rain, yellow dust rain, condensation, freezing and thawing, wetness and dryness, etc. due to environmental and geographical influences. They are exposed to an environment where contamination is inevitable.

In order to solve the above problems, various technologies are being researched and developed. Looking at these technologies, Patent No. 10-1170794 describes a coloring pigment mixed with water-soluble silicone acrylic resin, water, hardener, titanium oxide, and zinc oxide. A steel coating construction method using a heavy-duty anti-corrosion paint has been proposed.

The above prior art has the advantage of minimizing the generation of environmental pollutants by using eco-friendly products, but due to the use of water-soluble binders, water resistance is weak, so the surface of the coating film is easily contaminated when exposed to a wet environment for a long time, and corrosion performance is reduced. This has the problem of shortening durability.

In addition, in Registered Patent No. 10-1491459, a solvent-free type water-soluble epoxy resin and water-soluble coating agent that can improve workability, corrosion prevention, contamination prevention and durability while being eco-friendly by water-soluble paint and coating agent, improve corrosion performance, and coating agent. A steel coating construction method that prevents contamination of the surface of the coating film by smoothing the coating surface with polypropylene beads added has been proposed.

The above-mentioned prior art also has limitations in preventing contamination of the coating surface by smoothing the coating surface with polypropylene beads due to poor water resistance, which is a fundamental problem of the water-soluble epoxy binder itself.

In addition, Registration Patent No. 10-1209079 does not contain heavy metals or volatile organic compounds, and uses water as a diluent, so there is no concern about inhalation of heavy metals, poisoning by organic solvents, or fire during painting work, so work stability is excellent. , an eco-friendly anti-corrosion painting method for steel structures that demonstrates strong adhesion and rust prevention performance by using a mixture of water-soluble epoxy resins of different molecular weights has been proposed.

The above-mentioned prior art can secure basic rust prevention performance to a certain extent by aluminum oxide contained in the rust prevention paint, but this composition also suffers from a decrease in corrosion performance and surface damage due to poor water resistance in a humid environment, which is a fundamental problem of water-soluble epoxy resin. It has this problem of contamination.

In order to solve this problem, the present inventors, through No. 10-2110301, ‘Composition of eco-friendly composite ceramic coating for steel structures and method for manufacturing the same’, used solvent-free oil-based epoxy resin 96 to 96 to which a polar group was given, based on 100 parts by weight of all main components. 99.5 parts by weight of the main ingredient including 0.5 to 4 parts by weight of additives; And based on 100 parts by weight of the total curing agent components, 35 to 55 parts by weight of water-soluble epoxy curing agent, 8 to 12 parts by weight of coloring pigment, 15 to 25 parts by weight of fresh water, 6 to 10 parts by weight of potassium titanate, 2.5 to 5 parts by weight of airgel, and filler. It consists of a curing agent component containing 8 to 12 parts by weight and 1 to 5 parts by weight of an additive, and by further adding plate-shaped potassium titanate and hydrophobic silica airgel to the ceramic coating, the plate-shaped potassium titanate blocks the penetration of corrosion factors into the coating film. By improving the corrosion resistance of the coating agent and allowing the hydrophobic silica airgel to float to the top of the coating film to improve the fouling resistance of the coating agent, a coating material with excellent fouling resistance and adhesion strength has been proposed.

However, in the case of this composition, the miscibility with the water-soluble curing agent was improved by simply adding a polar group to the solvent-free epoxy resin, but there is a limit to ensuring complete miscibility with the water-soluble curing agent simply by giving the polar group to the epoxy resin.

Accordingly, an emulsifier is additionally used in the composition to ensure complete miscibility, but the use of an emulsifier has a fundamental problem in that it is accompanied by a decrease in the quality characteristics of the coating agent.

In particular, the low-temperature reactivity (below 10°C) between the non-solvent epoxy resin imparted with a polar group and the water-soluble hardener is poor, so when the working environment is low temperature (below 10°C), there is a disadvantage in that the corrosion resistance, acid resistance, and reactivity of the dried film are poor.

In addition, the existing composition of No. 10-2110301 is manufactured with a hardener base in which the components forming the coating film are included in the curing agent, and is different from the typical base-type paint in which the components forming the coating film are included in the main agent, so it can be used in the field. There are some areas where the coating process is difficult.

KR No. 10-1170794 (B1) (registered on July 27, 2012) KR No. 10-1491459 (B1) (registered on February 3, 2015) KR No. 10-1209079 (B1) (registered on November 30, 2012) KR No. 10-2110301 (B1) (registered on May 7, 2020)

The problem to be solved by the present invention is to provide a new eco-friendly hybrid ceramic coating composition that does not require the use of emulsifiers due to its high miscibility.

Another problem to be solved by the present invention is to provide a method for producing a new eco-friendly hybrid ceramic coating composition that has high miscibility and does not require the use of an emulsifier.

Another problem to be solved by the present invention is to provide a new eco-friendly hybrid ceramic coating composition that does not require the use of emulsifiers due to its high miscibility and includes coating film forming materials.

Another problem to be solved by the present invention is to increase the low-temperature reactivity (below 10°C) between the solvent-free oil-based resin imparted with a polar group and the water-soluble curing agent, thereby improving the corrosion resistance, reactivity, and acid resistance of the dried paint film even when working at low temperatures.

In order to solve the above problems, the present invention

Contains a main ingredient and a hardener ingredient,

Here, the main ingredients include 30 to 50 parts by weight of an oil-based resin imparted with a polar group, 11 to 16 parts by weight of a coloring pigment, 8 to 12 parts by weight of a plate-shaped organic or inorganic material, and 6 to 9 parts by weight of zinc phosphate, based on 100 parts by weight of the total main ingredients. parts by weight, 12 to 25 parts by weight of ceramic powder, 3 to 6 parts by weight of additives, 8 to 12 parts by weight of fresh water, and

The curing agent component includes 75 to 90 parts by weight of a water-soluble epoxy curing agent, 2 to 5 parts by weight of a curing accelerator, and 10 to 25 parts by weight of fresh water based on 100 parts by weight of the total curing agent components.

In the present invention, the polar group may be provided by an aminosilane-silica sol synthetic material.

In the present invention, the oil-based resin imparted with a polar group may be an epoxy resin imparted with a polar group, and the epoxy resin imparted with a polar group may be produced by the reaction of an epoxy resin and an aminosilane-silica sol synthetic material.

In the present invention, the aminosilane-silica sol composite material can be produced by the reaction of aminosilane, alcoholsilane, and silica precursor.

In one embodiment of the present invention, the polar group-imparted oil-based resin is prepared by adding a solvent-free epoxy resin and an amino silane-silica sol synthetic material, raising the temperature to 60° C. and maintaining it for 60 minutes while stirring, and then adding an ethyl silicate hydrolyzate. It was obtained by maintaining the reaction for 60 minutes, then adding the reaction catalyst sodium hydroxide (NaOH) dropwise to raise the temperature to 85°C, and then maintaining the reaction for 4 to 5 hours.

In one embodiment of the present invention, the polar group-imparted oil-based resin is 55 to 75 parts by weight of a solvent-free epoxy resin with an equivalent weight of 165 to 210 g/eq based on a total of 100 parts by weight in a 5L flask equipped with a thermometer, condenser, stirrer, and temperature increase device, After adding 15 to 20 parts by weight of amino silane-silica sol synthetic material and stirring at RPM 400 to 600, the temperature was raised to 60°C and maintained for 60 minutes. Then, 7 to 13 parts by weight of ethyl silicate hydrolyzate were added and maintained for 90 minutes, followed by reaction. 0.01 part by weight of catalyst is added dropwise, the temperature is raised to 85°C, the reaction is maintained for 5 hours, and the temperature is cooled to 50°C or lower to prepare an oil-based resin imparted with a polar group having an epoxy equivalent weight of 165 to 210. The amino silane-silica sol composite is prepared by adding 30 to 50 parts by weight of amino silane, 20 to 35 parts by weight of alcohol silane, and 20 to 35 parts by weight of silica precursor for 100 parts by weight in a 5L flask equipped with a thermometer, condenser, stirrer, and temperature increase device. After adding the mixture, the temperature was raised to 60°C and maintained for 30 minutes while stirring at RPM 1000 to 1200, then 0.01 parts by weight of reaction catalyst (nitric acid or phosphoric acid) was added dropwise, the temperature was raised to 90°C and the reaction was maintained for 6 to 7 hours. can be manufactured.

In one embodiment of the present invention, the silica precursor may be microsilica or nanosilica, but in the present invention, microsilica with an average diameter of 0.1 to 10 microns was used.

In one embodiment of the present invention, the alcohol silane may be one of methylsilanol, butylsilanol, and ethylkoxysilanol (Si(OC ₂ H ₅ ) ₄ ).

In one embodiment of the present invention, the aminosilane may be 3-aminopropyl trimethoxysilane (APTMS) or 3-aminopropyltriethoxysilane (APTES).

In one embodiment of the present invention, the reaction catalyst may be one of NH4OH and NaOH.

In one embodiment of the present invention, during the reaction, the pH value of the reaction solution must be maintained at an alkalinity of 9.5 to 11. If the PH value is below 9.5, the reaction speed is too slow, and if the PH value is above 11.5, the reaction may not occur.

In one embodiment of the present invention, the polar group-imparted oily resin prepared above has a weight average molecular weight of 400 to 1,200, an epoxy-equivalent weight of 165 to 210, a solid content of 96 to 99.99 parts by weight, a viscosity (25° C.) of 400 to 1,200 cps, It is preferable that the specific gravity (25°C) is 1.1 to 1.2 g/mL. If the weight average molecular weight of the polar group-imparted oil-based resin exceeds 1,200, the viscosity of the resin may increase excessively, which may result in poor curing due to poor compatibility with water-soluble epoxy curing agents. If the molecular weight is less than 400, problems such as deterioration of mechanical and chemical properties may occur. This can happen.

In the present invention, the polar group-imparted oil-based resin constituting the main ingredient can improve the water resistance, material adhesion, stain resistance, hardness, and mechanical and chemical properties of the eco-friendly hybrid ceramic coating by limiting the use of surfactants, especially the solvent-free oil-based resin. By imparting polarity to the resin to increase its miscibility with water, it has the advantage of excellent miscibility with water-soluble epoxy hardeners, allowing the curing reaction to proceed smoothly. The content is 30 to 50 parts by weight based on 100 parts by weight of the total main ingredients. Parts by weight, more preferably 35 to 45 parts by weight. If the content is less than 30 parts by weight of the main ingredient, the total resin content of the coating is lowered, which reduces material adhesion and corrosion prevention performance. If it exceeds 50 parts by weight, the amount of use of functional pigments and other additives is limited, which may lead to a decrease in the quality characteristics of the coating agent. there is.

In the present invention, the coloring pigment constituting the main component is used to impart color to the coating agent, and its content is preferably 11 to 16 parts by weight, more preferably 12 to 15 parts by weight, based on 100 parts by weight of the total main component. do. If the content of the coloring pigment is less than 11 parts by weight, the hiding power is reduced, and if it is more than 16 parts by weight, the effect of improving the hiding power is reduced compared to the amount used. Examples of coloring pigments include TiO2, cobalt blue, cyanine blue, carbon black, iron oxide black, iron oxide red, iron oxide sulfur, and oxide green. One or more of these can be used.

In the present invention, the plate-shaped organic and inorganic materials constituting the main components function to improve the performance of blocking the penetration of corrosion factors in the coating film and provide rigidity to the coating film, and after the coating agent is converted into a coating film, water, water vapor, and acid It can prevent the diffusion and penetration of alkaline ions, etc., and plays a role in improving the mechanical and chemical properties of various eco-friendly hybrid ceramic coatings by improving the strength and wear resistance of the coating film. The content is preferably 8 to 12 parts by weight, more preferably 8 to 10 parts by weight, based on 100 parts by weight of the total main ingredients. If the content of the plate-shaped organic and inorganic materials is less than 8 parts by weight, the density within the coating film of the dispersed plate-shaped organic and inorganic materials may decrease, which may reduce the corrosion factor blocking performance and mechanical and chemical performance. If the content exceeds 12 parts by weight, it may be reduced compared to the usage amount. The effect of increasing physical properties is minimal.

The plate-shaped organic and inorganic material contains 40 to 60 parts by weight of SiO ₂ , 20 to 40 parts by weight of Al ₂ O ₃ , 1 to 10 parts by weight of Fe ₂ O ₃ , and 5 to 15 parts by weight of K ₂ O based on 100 parts by weight of the total components, and has an oil absorption amount ( ml/100g) 45 to 55, true density (g/cm3) 2.8 to 3.2, and preferably an average particle size of 25 to 35㎛. The plate-shaped organic and inorganic materials must be plate-shaped, and if the average particle size range is wide or the oil absorption amount is outside the above range, it is difficult to control the viscosity when manufacturing the coating agent. In particular, if the organic and inorganic materials are rod-shaped or whisker-shaped, it blocks the penetration of corrosion factors. This may cause performance to deteriorate.

The microstructure of the plate-shaped organic and inorganic material is plate-shaped as shown in the electron microscope photo of Figure 2, and its hardness is very high, which can improve the property of blocking the penetration of deterioration factors and improve the rigidity of the coating film.

In the present invention, the zinc phosphate, which constitutes the main ingredient, plays a role in further improving the corrosion resistance of the eco-friendly hybrid ceramic coating, and its content is 6 to 9 parts by weight, based on 100 parts by weight of the total main ingredient. Preferably it is 7 to 8 parts by weight. If the zinc phosphate content is less than 6 parts by weight, the corrosion resistance performance is reduced, and if the zinc phosphate content is more than 9 parts by weight, the effect of improving the corrosion resistance performance is minimal.

In the present invention, the ceramic powder constituting the main ingredient serves to increase the volume of the dry film when applying the coating agent, and its content is preferably 12 to 25 parts by weight based on 100 parts by weight of the total main ingredient. Examples of ceramic powder include silica powder, talc, chlorine sulfate, potassium carbonate, etc. Among these, one or more types can be used, but there is no necessarily limitation thereto.

In the present invention, the additives constituting the main ingredients may preferably be 3 to 6 parts by weight based on 100 parts by weight of the total main ingredients. More specifically, based on 100 parts by weight of the total additive content, it may be preferable to include 2 to 10 parts by weight of an antifoamer, 2 to 10 parts by weight of a dispersant, 1 to 5 parts by weight of a wetting agent, 60 to 90 parts by weight of a flow prevention agent, and 8 to 16 parts by weight of a thickener.

In the above additive, the antifoaming agent serves to remove bubbles generated during the manufacture of the base material and to suppress or remove bubbles generated when applied after mixing the curing agent, and its content is 2 to 10 parts by weight based on 100 parts by weight of the total additive content. This may be desirable in terms of the effect of suppressing the generation of bubbles or preventing the antifoam agent from floating on the surface of the coating film, resulting in poor interlayer adhesion between coating films, and wrinkles on the surface of the coating film. Examples of antifoaming agents include one or more of TECH-407W, TECH-371W (Tech Polymer, China), and BYK-A555 (BYK, Germany), but are not necessarily limited thereto.

In the above additive, the dispersant serves to improve the dispersibility of color pigments, plate-shaped organic and inorganic materials, zinc phosphate, and ceramic powder, and its content is 2 to 10 parts by weight based on 100 parts by weight of the total additive components. It is desirable to deny it. If the content is less than 2 parts by weight of the additive component, the dispersion effect is reduced, and if it exceeds 10 parts by weight, the effect of improving dispersibility compared to the amount used is minimal. Examples of dispersants include one or more of BYK-180, BYK-111 (BYK, Germany), FDA-111, TECH-598 (Tech Polymer, China), and Dixpex CX 4320 (BASF, Germany). It can be used, and is not necessarily limited to this.

In the above additive, the wetting agent is used to ensure good wetting on the surface of the base material when applied after mixing the main component and the hardener component, and its content is preferably 1 to 5 parts by weight based on 100 parts by weight of the total additive components. If the content is less than 1 part by weight of the additive component, the wetting effect is reduced, and if it exceeds 5 parts by weight, phenomena such as cratering and pinholes may occur during application. Examples of wetting agents include one or more of BYK-378, BYK-3441, BYK-333 (BYK, Germany), TECH-244 (Tech Polymer, China), and Dixpex CX 4320 (BASF, Germany). It can be used, and is not necessarily limited to this.

In the above additive, the flow prevention agent serves to improve flow resistance during coating painting work, and its content is preferably 60 to 90 parts by weight based on 100 parts by weight of the total additive components. If the content is less than 60 parts by weight per 100 parts by weight of the total additive components, the effect of preventing flow is minimal, and if it exceeds 90 parts by weight, the flow resistance increases excessively, making spraying difficult. As an example of the flow prevention agent, one or more of MONORAL HR-300 and MONORAL HR-100 (hereinafter referred to as Korea HS-Chem) may be selected and used, but are not necessarily limited thereto.

In the above additive, the thickener serves to prevent precipitation of the pigment, and its content is preferably 8 to 16 parts by weight based on 100 parts by weight of the total additive components. If the content is less than 8 parts by weight of the additive component, the effect of preventing pigment precipitation is minimal, and if it exceeds 16 parts by weight, the spreadability of the coating film may be reduced due to excessive viscosity increase. Examples of the above thickener include one or more of OPTIBENT 940, OPTIBENT 987, OPTIBENT NT10 (German BYK), RM 2020, RM 825 (German DOW), and BS-1C-AC13 (Korea HS-Chem). You can select and use the above, but there is no limitation on this.

In the present invention, the fresh water constituting the main ingredient serves to adjust the viscosity of the coating agent, and its content is 8 to 12 parts by weight, preferably 9 to 11 parts by weight, based on 100 parts by weight of the total main ingredient. It is desirable. If the content of fresh water is less than 8 parts by weight based on 100 parts by weight of the total hardener components, the viscosity increases too much when mixing the coating agent, making mixing difficult. If it exceeds 12 parts by weight, the reactivity with the oil-based resin imparted with a polar group decreases and the viscosity of the coating agent becomes too low. Sedimentation may occur during storage.

In the present invention, the water-soluble epoxy curing agent constituting the curing agent component is not particularly limited as long as it is a curing agent that can be cured at room temperature with the solvent-free oil-based epoxy resin of the main component and has excellent miscibility, but is preferably curable at low temperatures in the winter and has a long pot life. In particular, it may be desirable to select and use a water-soluble epoxy curing agent that has excellent room temperature reactivity and has a solid content (%) of 50 to 100, a viscosity (20°C) of 100 to 1,000 cps, and an Equivalent Wt/H of 70 to 240. For example, the water-soluble epoxy curing agent may be polyamine, modified polyamine, polyetheramine, etc., and one or more of these may be selected and used, but are not necessarily limited thereto. It may be desirable for the content of the epoxy curing agent to be 75 to 90 parts by weight based on 100 parts by weight of the total curing agent components. If it is outside the above range, the curing of the epoxy resin contained in the main component does not proceed normally and the mechanical and chemical properties of the coating agent are affected. This may decrease, and problems such as drying defects may occur.

In the present invention, the curing accelerator constituting the curing agent component serves to improve the winter drying property of the coating agent, and its content is preferably 2 to 5 parts by weight based on 100 parts by weight of the total curing agent component. If the content of the curing accelerator is less than 2 parts by weight based on 100 parts by weight of the total hardener components, there is no effect on improving drying properties in winter. If it exceeds 5 parts by weight, the improvement in drying properties in winter is minimal compared to the amount used, and the visible time of the coating agent is reduced. It gets shorter.

In the present invention, the fresh water constituting the curing agent component plays a role in adjusting the viscosity of the coating agent, and its content is preferably 10 to 25 parts by weight based on 100 parts by weight of the total curing agent component. If the content of fresh water is less than 8 parts by weight based on 100 parts by weight of the total hardener components, the viscosity when mixing the coating agent becomes too high, making mixing difficult. If it exceeds 12 parts by weight, the viscosity of the coating agent becomes too low, which may cause precipitation during storage. .

In one aspect, the present invention

30 to 50 parts by weight of oil-based resin with a polar group, 11 to 16 parts by weight of coloring pigment, 8 to 12 parts by weight of plate-shaped organic and inorganic material, 6 to 9 parts by weight of zinc phosphate, 12 to 25 parts by weight of ceramic powder, 3 to 6 parts by weight of additives. Provided is an eco-friendly hybrid ceramic coating agent comprising a main composition consisting of 8 to 12 parts by weight of fresh water.

In another aspect, the present invention

30 to 50 parts by weight of oil-based resin with a polar group, 11 to 16 parts by weight of coloring pigment, 8 to 12 parts by weight of plate-shaped organic and inorganic material, 6 to 9 parts by weight of zinc phosphate, 12 to 25 parts by weight of ceramic powder, 3 to 6 parts by weight of additives. It provides a main composition for a ceramic coating agent consisting of 8 to 12 parts by weight of fresh water.

In another aspect, the present invention

A method for producing an oil-based resin imparted with a polar group is provided, which involves reacting an oil-based epoxy resin with an aminosilane-silica sol synthetic material.

In another aspect, the present invention

A method for producing an aminosilane-silica sol composite material is provided, which involves reacting aminosilane, alcoholsilane, and silica precursor.

In another aspect, the present invention

An eco-friendly hybrid ceramic coating agent is provided, which includes a base material containing an epoxy-silica hybrid oil-based resin and a water-soluble epoxy curing agent.

The eco-friendly hybrid ceramic coating composition manufactured according to the present invention has the disadvantages of existing oil-based coating materials such as non-eco-friendliness, water resistance and low quality performance, which are disadvantages of existing water-soluble coating materials, resulting in reduced corrosion prevention performance, softening and staining of the coating film when immersed, and material Problems such as low adhesion have been solved at once, and a dry coating film with excellent water resistance, adhesion, eco-friendliness, and impact resistance can be obtained by using a water-based and oil-based hybrid ceramic coating agent, and the addition of plate-shaped organic and inorganic materials and zinc phosphate prevents corrosion. It improves the ability to block penetration of elements and increases the strength and hardness of the coating film to protect it from external shocks, preventing physical and chemical corrosion, aging, and contamination of the structure.

In addition, the present invention eliminates the decline in quality characteristics of coatings due to the use of emulsifiers by perfectly mixing with water-soluble curing agents without using emulsifiers. As a result, a strong coating film with excellent material adhesion, water resistance, surface strength, and contamination resistance is formed. It is a useful invention that can maximize the service life of various structures by minimizing pollution from acid rain, yellow dust rain, dust, etc.

In addition, the present invention uses ceramic particles to impart a polar group to the oil-based resin, thereby allowing the ceramic particles to flow into the resin and improve the surface quality of the coating film.

In addition, the present invention provides a subject matter containing coating film constituents excluding the curing agent. This allows it to be easily used in field environments where the amount of base material is large and the amount of hardener is small.

Figure 1 is an electron microscope photograph of the interior of the water-based and oil-based eco-friendly hybrid ceramic coating of the present invention.
Figure 2 is an electron microscope photograph showing the particle structure of the acid-type organic and inorganic material (MICA) used in the present invention.

Hereinafter, the present invention will be described in detail through examples.

First, the eco-friendly hybrid ceramic coating containing (A) the main component and (B) the hardener component is in a form that can be applied with an airless spray, air spray, roller, or brush at room temperature by adjusting the viscosity without dilution or using water. It can be manufactured as a coating agent. In this case, the mixing ratio of (A) main component and (B) hardener component can be adjusted within an equivalent ratio of 1:1 ± 20%. In order to confirm the effect of the eco-friendly hybrid ceramic coating according to the present invention, an experiment was conducted on the following example.

Example 1

Amino silane-silica sol composite

Into a 5L flask equipped with a thermometer, condenser, stirrer, and temperature increase device, add 40 parts by weight of APTMS as amino silane, 30 parts by weight of methylsilanol as alcohol silane, and 30 parts by weight of microsilica with an average diameter of 1 micron as silica precursor. Then, while stirring at RPM 1100, the temperature was raised to 60°C and maintained for 30 minutes. Then, 0.01 parts by weight of nitric acid was added dropwise as a reaction catalyst, the temperature was raised to 90°C, and the reaction was maintained for 6 hours.

Synthesis of polar group-imparted oil-based resin

Into a 5L flask equipped with a thermometer, condenser, stirrer, and temperature increase device, add 70 parts by weight of solvent-free epoxy resin with an equivalent weight of 180 g/eq and 17 parts by weight of amino silane-silica sol synthetic material, then stir at RPM 400 to 600 and raise the temperature to 60°C. After raising the temperature to 85℃ and maintaining it for 60 minutes, 13 parts by weight of ethyl silicate hydrolyzate was added and maintained for 90 minutes. Then, 0.01 parts by weight of reaction catalyst NaOH was added dropwise. The temperature was raised to 85℃ and maintained for 5 hours. After that, the temperature was lowered to 50℃ or lower. By cooling, an oil-based resin imparted with a polar group having an epoxy equivalent weight of 180 was prepared.

According to the composition of the main ingredients as shown in Table 1, dispersant, antifoaming agent and wetting agent are added to the polar group-imparted oil resin shown above, then stirred at room temperature at RPM 1200 or higher for 10 minutes using a high-speed stirrer, and then colored pigment and plate-shaped The main ingredients were prepared by sequentially adding organic and inorganic materials, zinc phosphate, ceramic powder, anti-flow agent, and thickener, stirring at high speed for about 40 minutes at RPM 1800 to 2000, and then adding fresh water.

division Example Comparative example note One 2 3 4 5 6 One 2 3 4 5

main
my
castle
minute Polarized oil-based resin 30 40 50 40 40 40 - - - - - Equivalent weight 190g/eq, solid content 99.9 parts by weight (in-house synthesis) water soluble epoxy resin - - - - - - 40 - - - - KEM-128R
(Kukdo Chemical) Solvent-free epoxy resin - - - - - - - 40 40 - - YD-128
(Kukdo Chemical) Existing polar group-imparted oil-based resin - - - - - - - - - 40 - YI-RE-01
(Patent No. 10-2077046) Existing polar group-imparted oil-based resin - - - - - - - - - - 40 YI-RE-02
(Patent No. 10-2110310) dispersant 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 BYK-190 defoamer 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Tech-405W
BYK-066N (Comparative Example 3) humectant 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Tech-244
BYK-333 (Comparative Example 3) emulsifier - - - - - - - - - 0.5 - AS-801 (BASF) coloring pigment 13 13 13 13 13 13 13 13 13 13 13 TiO2 Plate-shaped organic and inorganic materials 9 9 9 6 12 12 9 9 9 9 9 SM-325 zinc
Phosphate 7 7 7 7 7 4 7 7 7 7 7 - ceramic powder 22 17 12 20 14 17 17 17 17 12 12 Silica #325 anti-flow agent 3 3 3 3 3 3 3 3 3 3 3 MONORAL HR-300,
MONORAL SD 10X (Comparative Example 3) thickener 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 BS-1C-A13 clear water 10 10 10 10 10 10 10 - - 9.5 10 water Epoxy thinner - - - - - - - 10 10 - - MIBK Total (g) 100 100 100 100 100 100 100 100 100 100 100
kyung
fury
my
castle
minute Water-soluble hardener 830 830 830 830 830 830 830 - 830 830 830 Anquamine 287 Oil-based hardener - - - - - - - 830 - - - KH-816 Hardening accelerator 30 30 30 30 30 30 30 30 30 30 30 KH-3001 clear water 140 140 140 140 140 140 140 140 140 140 140 water Epoxy thinner - - - - - - - - - - - MIBK Total (g) 100 100 100 100 100 100 100 100 100 100 100

※ Comparative Example 4: Manufacture of main ingredient using the resin applied in Patent No. 10-2077046.

※ Comparative Example 5: Manufacture of main ingredient using the resin applied in Patent No. 10-2110301.

Next, according to the composition of the curing agent component, a curing accelerator and fresh water were added to a polyamine-type curing agent as a water-soluble epoxy curing agent, and then stirred at room temperature at RPM 1200 or more for 20 minutes using a high-speed stirrer to prepare the curing agent component.

Subsequently, after preparing the main component and the curing agent component, eco-friendly hybrid ceramic coatings according to Examples 1 to 6 and Comparative Examples 1 to 5 containing the main component and the curing agent component were obtained based on the composition ratio in Table 1. .

In order to determine the quality characteristics of an eco-friendly hybrid ceramic coating formed from a composition containing the main component and hardener component of Examples 1, 2, 3, 4, 5, and 6 and Comparative Examples 1, 2, 3, 4, and 5, The main component and the hardener component were mixed so that the equivalence ratio was 1:1 ± 20%, and for ease of airless spraying, 0 to 10 parts by weight of fresh water was mixed as a diluent to prepare the coating agent required for airless spraying. To evaluate the film performance of the coating agent, test specimens were prepared as shown in Table 2.

NO. Test Items Dimensions of the test piece (unit: mm) number note One salt spray
test Room temperature drying test piece 70x150x3.2 3 steel Low-temperature dry test piece 2 Neutering depth 100x100x100 3 mortar 3 moisture permeability 150 3 mortar 4 Contamination resistance performance test 300x300x3.2 3 steel 5 water resistance test 70x150x3.2 3 steel 6 Abrasion resistance test 100x100 3 coating agent 7 Adhesion strength test 70x150x3.2 3 steel 70x70x20 3 mortar 8 Miscibility (base + hardener) 500g One coating agent 9 Storage stability after mixing 500g One coating agent 10 reactivity
(dryness) room temperature 70x150x3.2 One steel low temperature 11 acid resistance test Room temperature drying test piece 70x150x3.2 3 steel Low-temperature dry test piece 12 Alkali resistance test 70x150x3.2 3 steel

※ Room temperature: above 10℃. Low temperature: below 10℃

In order to evaluate the film performance using the coating agent prepared in this way, first, the steel specimen is surface treated with a cold-rolled steel sheet (KS D 3512) using a shot blast pre-treatment machine to a pre-treatment standard of SSPC SP10 or higher and a roughness of 25 to 75 ㎛, For the concrete specimen, the mortar (7.3.1 of KS F 2476) surface was grinded, and then each coating prepared above was applied with an airless sprayer at a relative humidity of 85% or less and a temperature of 15 to 35°C to maintain the same dry film thickness. After painting (dry film thickness is not specified and varies depending on the use of the coating agent, application area, etc.), the film was dried for 7 days at room temperature and low temperature (salt spray, reactivity, acid resistance test), and then the film properties were tested (but abrasion resistance). In the case of performance test specimens, the coating is applied several times to a film thickness of 1 mm)

The coating film physical property test was evaluated according to the coating film physical property evaluation method as follows.

1) Salt spray test

The specimen prepared above was tested according to KS D 9502 (neutral, acetic acid, cass spray test), and the coating film was observed after the test for 300 hours. At this time, after observing rust, swelling, and peeling of the coating film, the values were expressed from the lowest 1 to the highest 10.

2) Neutering depth

The specimen prepared above was subjected to a neutralization depth test in accordance with KS F 4936 (concrete protective coating material), and then the neutralization depth (mm) was measured.

3) Water vapor permeability

The specimen prepared above was subjected to a moisture permeability test in accordance with KS F 4936 (concrete protective coating material), and then the moisture permeability (g/㎡·day) was measured.

4) Contamination resistance performance test

The specimens prepared above were tested according to the test methods of KS M 3802 and KS A0063. At this time, after observing rust, swelling, and peeling of the coating film, the values were expressed from the lowest 1 to the highest 10.

5) Water resistance test

The specimen prepared above was immersed in distilled water at 60°C for 30 days. At this time, it was taken out every 24 hours to check for any abnormalities on the surface of the coating film (smearing, softening, swelling, cracks, peeling, etc.) and then marked with a value from the lowest 1 to the highest 10. (To promote and observe water resistance performance, 60°C distilled water observed deposition).

6) Wear resistance test

The specimen prepared above was tested using a CS-17 wheel, 1kg load, and 1000 cycles in accordance with KS M ISO 7784-2, and the amount of wear of the coating film was expressed numerically.

7) Adhesion strength test

The adhesion strength of the steel specimen prepared above was measured according to the test method of ASTM D4541-09. Mortar, the specimen prepared in the above example was subjected to an adhesion test according to KS F 4936 (concrete protective coating material), and then the adhesion strength (N/mm ² ) was measured.

8) Miscibility test

After mixing the main ingredients and hardener ingredients prepared above at the specified mixing ratio, the degree of miscibility was visually observed and expressed as a number from the lowest 1 to the highest 10.

9) Storage stability after mixing

The solution prepared by mixing the main component and the hardener component in the specified mixing ratio was diluted with water to 10% by weight (Comparative Example 2: epoxy thinner), and after 1 hour at room temperature, the degree of layer separation was visually observed, ranging from a minimum of 1 to a maximum of 1. It is expressed as a number of 10.

10) Reactivity (drying)

After mixing the main ingredients and hardener ingredients prepared above in the specified mixing ratio, form a wet film with a film thickness of 76㎛ using a film applicator, and then measure the degree of drying after 24 hours at room temperature (above 10℃) and low temperature (below 10℃). After observation, the values were expressed from the lowest to 1 to the highest to 10.

11) Acid resistance test

The specimen prepared above was tested according to the test method of KS M 5307, and the coating film was observed after immersion in 10% H2SO4 solution for 168 hours. At this time, swelling, peeling, cracks, etc. of the coating film were observed and expressed on a scale from the lowest of 1 to the highest of 10.

12) Alkali resistance test

The specimen prepared above was tested according to the test method of KS M 5307, and the coating film was observed after immersion in a 10% NaOH solution for 168 hours. At this time, swelling, peeling, cracks, etc. of the coating film were observed and expressed on a scale from the lowest of 1 to the highest of 10.

The results of evaluating the physical properties of the specimen by the above method are shown in Table 3.

Evaluation items Example Comparative example One 2 3 4 5 6 One 2 3 4 5 Salt Spray Test room temperature 8 10 10 8 10 6 6 10 measurement
Impossible 9 9 low temperature 6 10 10 6 10 5 4 10 measurement
Impossible 6 6 Neutering depth 0.2 0 0 0.4 0 0 0.5 0 measurement
Impossible 0 0 moisture permeability 21 12 12 32 12 12 30 11 measurement
Impossible 14 14 Contamination resistance performance test 10 10 10 10 10 10 6 10 measurement
Impossible 10 10 Water resistance test 10 10 10 10 10 10 5
(buried) 10 measurement
Impossible 10 10 Abrasion resistance test 120 92 89 91 92 92 154 88 measurement
Impossible 92 89 Adhesion strength
(MPa) steel 6.7 7.8 7.9 7.6 7.2 7.7 4.7 7.9 measurement
Impossible 7.0 7.2 mortar 2.7 2.7 2.8 2.5 2.6 2.7 1.8 2.7 measurement
Impossible 2.7 2.7 Mixability
(base + hardener) 9 9 9 9 9 9 10 10 One 9 9 Storage stability after mixing 9 9 9 9 9 9 10 10 One 6 6 reactivity
(dryness) room temperature 10 10 10 10 10 10 10 10 reaction
error 10 10 low temperature 10 10 10 10 10 10 9 10 reaction
error 7 7 acid resistance
test room temperature 10 10 10 10 10 10 7 10 measurement
Impossible 10 10 low temperature 10 10 10 10 10 10 5 10 measurement
Impossible 7 7 Alkaline resistance test 10 10 10 10 10 10 10 10 measurement
Impossible 10 10

※ Comparative Example 1: Water-soluble epoxy coating material. Comparative Example 2: Oil-based epoxy coating material

As summarized in Table 3 above, the use of an oil-based resin with a self-synthesized polar group contributes to improving the physical properties such as water resistance, corrosion resistance (salt spray test), abrasion resistance, adhesion strength, and acid resistance, which are the disadvantages of water-soluble epoxy resin. It can be seen that, in particular, it has excellent low-temperature reactivity compared to Comparative Examples 4 and 5 using the existing polar group-imparted solvent-free resin, contributing to the improvement of physical properties such as salt spray test and acid resistance.

In addition, it can be seen that the storage stability is greatly improved after mixing compared to Comparative Examples 4 and 5 using the existing oil-based resin imparted with a polar group, and the use of plate-shaped organic and inorganic materials contributes to improving the physical properties of neutralization depth and moisture permeability. It can be seen that the use of zinc phosphate contributes to improving the physical properties of the salt spray test (corrosion prevention performance). In addition, in the case of general oil-based solvent-free epoxy resins, the miscibility with water-soluble epoxy hardeners is very poor, making it impossible to form a coating film.

In the case of the salt spray test, as seen in the evaluation results of Examples 2, 3, and 5, the performance of plate-shaped organic and inorganic materials and zinc phosphate in blocking the penetration of corrosion factors and improving the corrosion resistance performance was better than that of Examples 1, 4, and 6. It can be seen that it has greatly improved, and when compared to Comparative Example 2 (oil-based epoxy), it can be seen that there is no decrease in physical properties, and when compared to Comparative Examples 4 and 5 using existing polar group-imparted resins, it can be seen that the corrosion prevention performance is somewhat improved. there is. In particular, in the case of specimens dried at low temperature, it can be seen that the corrosion prevention performance was greatly improved compared to Comparative Examples 4 and 5 using existing resins. This is believed to be a result of improved low-temperature reactivity and material adhesion between the new resin and the water-soluble hardener. In the case of Comparative Example 1, it can be seen that salt spray properties are reduced due to the disadvantages of the water-soluble binder itself, which are poor water resistance and reduced adhesion strength. In Example 1, it can be seen that the salt water resistance is poor due to the low adhesion strength due to the low content of the oil-based resin imparting a polar group.

In the case of the neutralization depth and moisture permeability test, as seen in the evaluation results of Examples 2, 3, 5, and 6, the penetration blocking properties of the plate-shaped organic and inorganic materials and the improvement of the rigidity of the coating film were affected by Examples 1, 4, and Comparative Example 1. It can be seen that it has greatly improved, and when compared to Comparative Example 2 (oil-based epoxy), it can be seen that there is no decrease in physical properties, and when compared to Comparative Examples 4 and 5 using the existing polar group-imparted resin, there is a slight difference, but some improvement can be seen. . It is believed that this is due to the greater influence of plate-shaped organic and inorganic materials than resin. In the case of Example 1, the content of the oil-based resin imparting a polar group is lower than the content of the plate-type organic and inorganic material, and thus the moisture permeability is judged to be somewhat low. In the case of Comparative Example 1, the neutralization depth and moisture permeability are lower due to the influence of poor water resistance, which is a disadvantage of the water-soluble binder itself. You can see the deterioration.

In the case of the contamination resistance test, as can be seen from the evaluation results of Examples 1 to 6 and Comparative Examples 4 and 5, the water resistance and rigidity of the coating film were improved as the oil-based resin imparted with a polar group was applied, which was better than that of Comparative Example 1 (water-soluble epoxy). It can be seen that it has greatly improved, and when compared to Comparative Example 2 (oil-based epoxy), it can be seen that there is no decrease in physical properties.

In the case of the water resistance test, as can be seen from the evaluation results of Examples 1 to 6 and Comparative Examples 4 and 5, a self-synthesized polar group-imparted oil-based resin was used, which solved the problem of poor water resistance, which is a drawback of the water-soluble epoxy binder itself. Comparative Example 1 It can be seen that it has greatly improved, and when compared to Comparative Example 2 (oil-based epoxy), it can be seen that there is no decrease in physical properties.

In the case of the adhesion strength test, as can be seen from the evaluation results of Examples 1 to 6 and Comparative Examples 4 and 5, it was seen that both the steel and mortar surfaces were greatly improved compared to Comparative Example 1 (water-soluble epoxy) due to the influence of the application of the polar group-imparted oil-based resin. When compared to Comparative Examples 4 and 5 using existing polar group-imparted resins, it can be seen that the adhesion to the steel surface is somewhat improved, and it is believed that the adhesion of the resin is improved by the amino silane and silica sol synthetic material. However, in the case of the concrete surface, the concrete itself was broken, so no difference in adhesion could be seen. Even when compared with Comparative Example 2 (oil-based epoxy), it can be seen that there is no decrease in physical properties.

In the case of the above miscibility, the miscibility is slightly lower than that of Examples 1 to 6 using a self-synthesized oil-based resin, Comparative Example 4, Comparative Example 1 using a pentavalent water-soluble epoxy resin and a water-soluble curing agent, and Comparative Example 2 using an oil-based epoxy and an oil-based curing agent. (Slight layer separation was observed when left at room temperature after mixing), and it can be seen that the reactivity (drying) after coating was normal, the same as in Comparative Examples 1 and 2.

In the case of storage stability after mixing, the same results as the above miscibility test were seen at the beginning of mixing, but in Comparative Examples 4 and 5 using the existing polar group imparting resin, layer separation phenomenon appeared after about 40 minutes of storage at room temperature. there was. This is believed to be the result of diluting the mixed solution with water (10% by weight), which lowered the viscosity of the mixed solution and made it easier for layer separation to occur.

In the case of reactivity (drying) at room temperature (10°C or higher), there were no abnormalities in all of Examples 1 to 6 and Comparative Examples 1, 2, 4, and 5, but in the case of reactivity (drying) at low temperature (10°C or lower) It can be seen that all of Examples 1 to 6 and Comparative Examples 1 and 2 have the same reactivity as at room temperature, but in the case of Comparative Examples 4 and 5, low temperature reactivity is poor. This is believed to be a phenomenon that occurs due to poor low-temperature curing properties between existing polar group-imparted oil-based resins and water-soluble hardeners.

In the case of the acid resistance test, as can be seen from the evaluation results of Examples 1 to 6 and Comparative Examples 4 and 5, it can be seen that it is greatly improved compared to Comparative Example 1 due to the influence of the polar group-imparted oil-based resin. In particular, in the case of specimens dried at low temperature, the existing It can be seen that acid resistance is greatly improved compared to Comparative Examples 4 and 5 using resin. This is believed to be a result of improved low-temperature reactivity between the new resin and the water-soluble hardener.

Even when compared with Comparative Example 2 (oil-based epoxy), it can be seen that there is no decrease in physical properties.

In the case of the alkali resistance test, it can be seen that there were no abnormalities in all of Examples 1 to 6 and Comparative Examples 4 and 5. Even when compared with Comparative Examples 1 and 2, it can be seen that there is no decrease in physical properties.

In Comparative Example 3, the miscibility of the oil-based solvent-free epoxy resin and the water-soluble curing agent was very poor, making it impossible to form a coating film, making overall physical property testing impossible.

As explained above, according to the present invention

The composition and manufacturing method of a water-based and oil-based combined eco-friendly hybrid ceramic coating using an oil-based resin imparted with a polar group have been described through examples, and the excellence of the physical properties has been confirmed. However, the present invention is not necessarily limited to the above examples. , various substitutions, modifications and changes are possible without departing from the technical spirit of the present invention.

Claims (7)

Contains a main ingredient and a hardener ingredient,
Here, the main ingredients include 30 to 50 parts by weight of an oil-based resin imparted with a polar group, 11 to 16 parts by weight of a coloring pigment, 8 to 12 parts by weight of plate-shaped mica, and 6 to 9 parts by weight of zinc phosphate, based on 100 parts by weight of the total main ingredients. parts by weight, 12 to 25 parts by weight of ceramic powder, 3 to 6 parts by weight of additives, 8 to 12 parts by weight of fresh water, and
The curing agent component includes 75 to 90 parts by weight of a water-soluble epoxy curing agent, 2 to 5 parts by weight of a curing accelerator, and 10 to 25 parts by weight of fresh water, based on 100 parts by weight of the total curing agent components,
Here, the oil-based resin to which the polar group is given is an eco-friendly hybrid ceramic coating agent, characterized in that it contains an epoxy resin and an aminosilane-silica sol synthetic material. delete According to paragraph 1,
Aminosilane-silica sol composite is an eco-friendly hybrid ceramic coating produced by the reaction of aminosilane, alcoholsilane, and silica precursor. According to claim 1 or 3,
An eco-friendly hybrid ceramic coating agent, characterized in that the oil-based resin imparted with a polar group is an oil-based resin imparted with a polar group having an epoxy equivalent weight of 165 to 210. According to paragraph 3,
An eco-friendly hybrid ceramic coating, characterized in that the silica precursor is microsilica of 0.1 to 10 microns. According to claim 1 or 3,
The oil-based resin to which a polar group is given has a weight average molecular weight of 400 to 1,200, an epoxy-equivalent weight of 165 to 210, a solid content of 96 to 99.99 parts by weight, a viscosity (25°C) of 400 to 1,200 cps, and a specific gravity (25°C) of 1.1 to 1.2 g/mL. An eco-friendly hybrid ceramic coating agent characterized by:
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