KR20250019296A - Method of manufacturing heat-resistant non-combustible adhesive that withstands high temperatures of 1300 degrees or more and non-combustible adhesive manufactured thereby - Google Patents

Abstract

The present invention relates to a method for manufacturing a high-temperature ceramic adhesive binder with enhanced adhesive strength, comprising: (a) a step of mixing at least one of liquid potassium silicate, liquid lithium silicate, potassium silicate, and colloidal silicate into liquid sodium silicate as a main component, and preparing a mixture in an amount of 60 to 75 wt% based on 100 wt% of the high-temperature adhesive binder composition manufactured through steps a to d below; (b) a step of adding and mixing at least one of a silane coupling agent or an aluminate coupling agent in an amount of 0.5 to 2.5 wt% to the mixture of step a; (c) a step of adding and mixing 15 to 30 wt% of at least one of kaolin, aluminum phosphide, zinc oxide, phosphorus oxide, metal oxide, expanded perlite, expanded vermiculite, calcium carbonate, silicon dioxide, talc, and clay as a ceramic filler to the mixture of step b; and (d) a step of adding and mixing 2 to 3 wt% of an acrylic resin emulsion and 1 to 5 wt% of an epoxy resin emulsion to the mixture of step c.

Description

Method for manufacturing heat-resistant non-combustible adhesive that withstands high temperatures of 1300 degrees or more and non-combustible adhesive manufactured thereby

The present invention relates to a method for manufacturing a ceramic high-temperature adhesive binder with enhanced adhesive strength, and a high-temperature adhesive binder manufactured thereby. More specifically, the present invention relates to a method for manufacturing a ceramic high-temperature adhesive binder with enhanced adhesive strength, which is capable of withstanding extremely high temperatures such as 1300 degrees Celsius when a Styrofoam fire occurs, and which is safe because it does not catch fire and therefore does not generate toxic gases, and a high-temperature adhesive binder manufactured thereby.

The characteristic of recent large-scale fire accidents is that when a fire occurs, a large amount of smoke and toxic gases are emitted due to combustion of interior materials, leading to large-scale disasters that result in numerous casualties. The reason for such large-scale disasters is that the use of various polymer materials for interior materials makes it difficult to evacuate due to smoke and toxic gases generated during a fire.

The cause of smoke and toxic gases is the combustion of various organic polymer materials used as interior and exterior materials for buildings, vehicles, furniture, and home appliances. The solution is to make the polymer materials fire-resistant or non-combustible, thereby preventing the rapid spread of fire and extinguishing the fire early, thereby minimizing damage to life and property. In addition, as regulations on flammability of synthetic resins, rubber, fibers, and paper are gradually being strengthened worldwide, the need for fire-resistant or non-combustible materials to respond to this is greatly emphasized.

For example, fire doors in buildings are mainly used as entrance doors or emergency exit doors in general houses, apartments, factories, offices, prefabricated buildings, etc., and are usually made of sturdy metal materials to prevent external fires from spreading indoors or internal fires from spreading to the outside. In addition, they must have physical properties that ensure that the entrance doors or emergency doors do not burn or deform even due to the strong internal heat in the event of a fire.

Recently, large-scale fires have occurred frequently in buildings that use Styrofoam as the exterior wall material for dryvit buildings, causing unfortunate damage to life and property, becoming an issue.

Accordingly, the use of non-combustible materials is being legislated for the construction of building exterior walls using the dryvit method, and demand for non-combustible adhesives that can withstand high temperatures of 1,300 degrees, such as Styrofoam fires, is expected to increase rapidly.

However, in reality, most urethane foam adhesives are used to bond panels and honeycomb cores. However, these urethane foam adhesives have a limiting oxygen index (LOI) of 17%, which does not correspond to a fire-resistant material with a limiting oxygen index exceeding 27%. In addition, they have a low temperature resistance with an ignition point of around 50 degrees, and in particular, they emit toxic gases when burned, which is recognized as a fatal problem.

In addition, in the case of sandwich panels that use organic or inorganic core insulation between metal plates, urethane foam adhesives are used to bond the metal plates and cores. However, these urethane foam adhesives are easily combusted in case of fire and emit toxic gases, which acts as a factor in reducing the fire resistance of the panel.

Accordingly, there are growing calls for the development of a ceramic high-temperature adhesive binder with enhanced adhesive strength that is heat-resistant and non-flammable enough to withstand a 1300-degree fire and does not generate toxic gases.

Accordingly, the present invention has been made to solve the above problems, and the purpose of the present invention is to provide a method for manufacturing a ceramic high-temperature adhesive binder having enhanced adhesive strength and water resistance, and being able to withstand extremely high temperatures such as 1300 degree flames generated by a Styrofoam fire, and not only that it does not catch fire and therefore does not generate toxic gases, but also has safe adhesive strength and a high-temperature adhesive binder manufactured thereby.

In order to achieve the above objects, the present invention comprises: (a) a step of mixing at least one of liquid potassium silicate, liquid lithium silicate, potassium silicate, and colloidal silicate into liquid sodium silicate as a main component, and preparing a mixture in an amount of 60 to 75 wt% based on 100 wt% of a high-temperature adhesive binder composition prepared through steps a to d below; (b) a step of adding and mixing 0.5 to 2.5 wt% of at least one of a silane coupling agent or an aluminate coupling agent into the mixture of step a; (c) a step of adding and mixing 15 to 30 wt% of at least one of kaolin, aluminum phosphide, zinc oxide, phosphorus oxide, metal oxide, expanded perlite, expanded vermiculite, calcium carbonate, silicon dioxide, talc, and clay as a ceramic filler into the mixture of step b; And (d) a step of adding and mixing 2 to 3 wt% of an acrylic resin emulsion and 1 to 5 wt% of an epoxy resin emulsion to the mixture of step c.

In addition, according to one embodiment, based on 100 wt% of the high-temperature adhesive binder composition manufactured through steps a to d, the method further includes: (e) adding and mixing 1 to 3 wt% of zinc phosphate or red soil, and then dispersing the mixture through a homogenizer.

In addition, a ceramic high-temperature adhesive binder having enhanced adhesive strength manufactured according to one embodiment of the above manufacturing method is provided.

As described above, the adhesive binder of the present invention not only has improved adhesiveness and water resistance, but also can withstand extremely high temperatures of 1300 degrees or higher, such as in a Styrofoam fire, and does not generate toxic gases as it does not catch fire, thereby significantly improving safety.

In addition, it can be applied not only to general buildings but also to related industries that use facilities in ultra-high temperature environments, so it has an excellent effect of drastically reducing damage to precious lives and property.

Figure 1 is a photographic image of a test on the non-flammability of a ceramic high-temperature adhesive binder with enhanced adhesive strength of the present invention.
Figures 2 to 6 are test results proving the non-combustibility of a specimen manufactured according to the present invention.

The terminology used herein is only used to describe particular embodiments and is not intended to be limiting of the present invention. The singular expression includes the plural expression unless the context clearly indicates otherwise. As used herein, the terms "comprises" or "has" or "comprising" and the like are intended to specify the presence of a feature, number, step, operation, component, part or combination thereof described in the present specification, but should be understood to not exclude in advance the possibility of the presence or addition of one or more other features, numbers, steps, operations, components, parts or combinations thereof.

Unless otherwise defined herein, 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 defined in commonly used dictionaries should be interpreted as having a meaning consistent with their meaning in the context of the relevant technology and should not be interpreted in an idealized or overly formal sense, unless expressly defined otherwise herein.

Hereinafter, the ceramic high-temperature adhesive binder with enhanced adhesive strength of the present invention and the high-temperature adhesive binder manufactured thereby will be described in more detail.

The present invention can be manufactured by the following steps.

Step a: As a main component of the present invention, at least one of liquid potassium silicate, liquid lithium silicate, liquid potassium silicate, or colloidal silicate is mixed with liquid sodium silicate (application example: KS No. 2/3, molar ratio 3.1-3.3), to prepare a binder mixture of 60 to 75 wt% (based on 100 wt% of the high-temperature adhesive binder composition manufactured through step a to step d below).

Sodium silicate is one of the representative inorganic binder materials, and unlike organic adhesives obtained from petrochemicals, it has high thermal stability and is environmentally friendly, so it is widely used as a heat-resistant, chemical-resistant, and waterproof coating agent.

In particular, the above liquid sodium silicate is used as one of the binder materials of the present invention, and as the amount of moisture decreases, the viscosity of the solution rapidly increases and it has adhesive strength, so when applied to a surface to be bonded, a smooth film like glass is obtained, and at the same time, it is excellent in effect as an adhesive.

The above liquid sodium silicate has the physicochemical characteristics of good heat resistance and excellent adhesive performance, and is inexpensive. Liquid potassium silicate has the characteristics of good compatibility, less efflorescence, and relative stability at high temperatures compared to liquid sodium silicate.

In addition, liquid lithium silicate has a lower alkali content than liquid sodium silicate or liquid potassium silicate, which is advantageous in improving water resistance and heat resistance.

In addition, liquid potassium silicate is a polymer compound that is advantageous in improving the rheological properties, electrical properties, compressibility and adhesion of water glass as well as hardness and strength.

In addition, when liquid colloidal silicate is added, effects such as increased contamination resistance, hardness, water resistance, heat resistance, and flame retardancy can be obtained.

For the reasons described above, one or a mixture of liquid sodium silicate, liquid potassium silicate, liquid lithium silicate, liquid potassium silicate, and liquid colloidal silicate is used in combination with liquid sodium silicate.

According to one embodiment, a binder solution is prepared by mixing 0.4 to 0.6 parts by weight of a mixture of liquid potassium silicate, liquid lithium silicate, liquid potassium silicate, and liquid colloidal silicate relative to 1 part by weight of liquid sodium silicate, and then preparing a binder solution of 60 to 75 wt% based on 100 wt% of the high-temperature adhesive binder composition prepared through steps a to d below.

That is, the mixing ratio of liquid potassium silicate, liquid lithium silicate, liquid potassium silicate and liquid colloidal silicate to the liquid sodium silicate is suitably 0.4 to 0.6 parts by weight of liquid potassium silicate, liquid lithium silicate, liquid potassium silicate, liquid colloidal silicate or a mixture thereof based on 1 part by weight of liquid sodium silicate.

Here, the content range of the two binder materials indicates a relative suitable range for exhibiting strong adhesive force, and if it exceeds the above range, there is a concern that the mutual adhesive force of the two binder materials may be weakened.

Step b: Add and mix at least one of a silane coupling agent or an aluminate coupling agent in an amount of 0.5 to 2.5 wt% to the mixture of step a.

The above silane coupling agent has one side of the molecule that forms a surface bond with an inorganic filler or glass fiber mixed into the polymer, and the other side has an affinity for the matrix resin, so that the dispersibility and the adhesiveness of the interface between the inorganic filler or glass fiber and the matrix polymer are improved, thereby playing a role in improving the bonding strength.

In one embodiment, the silane coupling agent can be a polydimethylsiloxane solution, and the silane coupling agent can be replaced with an aluminate coupling agent.

Here, if the content of the coupling agent is added below the above range, it may be difficult to obtain sufficient bonding strength, and if it exceeds the above range, there is a concern that the expected surface bonding strength may not be obtained.

According to one embodiment, a coupling agent material, either a silane coupling agent or an aluminate coupling agent, may be added to the binder mixture prepared in step a, and then stirring and mixing may be performed for 30 minutes or more.

Step c: Add and mix 15 to 30 wt% of at least one of kaolin, aluminum phosphide, zinc oxide, phosphorus oxide, metal oxide, expanded perlite, expanded vermiculite, calcium carbonate, silicon dioxide, talc, and clay as a ceramic filler to the mixture of step b.

Here, the ceramic filler forms a film on the surface of the resin by diluting the combustible gas by the inert gas during combustion and decomposing the inorganic compound by heat, thereby forming a by-product reaction with the acrylic resin or epoxy resin (step d) described below, thereby blocking the access of oxygen necessary for combustion, reducing cooling of the material and the production of thermal decomposition products by the endothermic reaction, and having stability at high temperatures.

According to one embodiment, to the mixture prepared in step b, one or more of kaolin, aluminum phosphide, zinc oxide, phosphorus oxide, metal oxide, expanded perlite, expanded vermiculite, calcium carbonate, silicon dioxide, talc, and clay (when two or more substances are mixed, they may be mixed in the same ratio, for example) may be added in appropriate amounts, and stirring and mixing may be performed for 1 hour or more.

If the content of the ceramic filler is less than 15 to 30 wt%, the added ceramic filler may act as a seed, causing other mixtures added later to stick to it, causing the particles to become enlarged and the workability to deteriorate when the paint is applied.

In addition, if the content of the ceramic filler exceeds the range of 15 to 30 wt%, there is a concern that a problem may arise in which the non-combustibility performance is not sufficiently exhibited due to the excess content.

Step d : Add and mix 2 to 3 wt% of acrylic resin emulsion and 1 to 5 wt% of epoxy resin emulsion to the mixture of step c.

By adding a certain amount of the above acrylic resin and epoxy resin emulsion, the adhesive strength of the adhesive binder to which the present invention is applied can be improved. That is, the above acrylic resin and epoxy resin are binder resins used for water-based paints and impart excellent film-forming function.

The above acrylic resin emulsion is a common one used as a paint, containing acrylic, melamine, and epoxy resin as main components, and has excellent adhesion to materials and excellent chemical resistance, water resistance, corrosion resistance, hardness, gloss, and gloss retention properties.

Meanwhile, the above acrylic resin emulsion is a type of glossy water-based paint sold under the name Akron by Samhwa Paint and under the name ‘Glorytex’ by Jevipyo Paint, and can be purchased through these.

The above film formation function is a performance in which the particle nature of the film surface disappears after drying at a certain temperature or higher, and also in which fine cracks, etc. do not occur during drying. The drying temperature (MFT) range for film formation is not particularly limited.

Meanwhile, in addition to the acrylic resin and epoxy resin, if a silicone-based resin is added, the surface of the substrate to which the present invention is applied can be provided with additional slipperiness or water repellency.

More specifically, in this step, 2 to 3 wt% of acrylic resin emulsion and 1 to 5 wt% of epoxy resin emulsion are added in small portions to the mixture prepared in step c, and stirred and mixed for 30 minutes or more.

Step e : Add and mix 1 to 3 wt% of zinc phosphate or red soil, and disperse through a homogenizer.

By adding a certain amount of the above zinc phosphate or red clay, the adhesion, rust prevention, and ultraviolet stability of the paint surface to which the present invention is applied are improved.

According to one embodiment, in this step, 1 to 3 wt% of zinc phosphate or 1 to 3 wt% of red clay is added and mixed in small amounts to the mixture prepared in step d to increase adhesion, rust resistance, and ultraviolet stability, and particles that are not sufficiently mixed and clumped together are nano-dispersed using a homogenizer for 3 hours or more, thereby preventing the phenomenon of the non-flammability of the adhesive binder of the present invention from being reduced.

In this way, a ceramic high-temperature adhesive binder with enhanced adhesive strength is manufactured according to the steps described above.

The ceramic high-temperature adhesive binder with enhanced adhesive strength manufactured as described above has excellent heat-resistant and non-combustible performance even at a high temperature of 1300 degrees, and therefore can be widely applied to, but is not limited to, fire doors, building dryvit, bonding of non-combustible sandwich panels, tile bonding curtain walls, inter-floor fire compartments, building crack repair agents, building filling putty agents, building structures, lightweight bricks (ALC, CLC), lightweight wall assembly adhesives, industrial metal/ceramic adhesives, and electrical and electronic product component assembly adhesives.

The attached drawing 1 is a photographic image of a fire-retardant performance test of a ceramic high-temperature adhesive binder with enhanced adhesive strength of the present invention.

According to one embodiment, a non-combustible board specimen for dryvit was manufactured by mixing inorganic foam particles with a ceramic high-temperature adhesive binder having enhanced adhesive strength of the present invention, and the same point of the non-combustible board specimen manufactured as described above was continuously heated using a gas torch.

As shown in the photographic image of Fig. 1, even when the same point was heated to 1300 degrees by a gas torch, the point heated by the gas torch was only carbonized black, and no flame occurred or burned, confirming the excellent non-flammability of the adhesive binder manufactured by the present invention.

Therefore, for example, when the ceramic high-temperature adhesive binder with enhanced adhesive strength of the present invention is applied to a non-combustible board for dryvit, even if a large-scale fire occurs due to a gas leak or the like, the flames do not spread to the non-combustible board, so that precious human lives can be safely protected from the flames, and the flame spread speed can be significantly slowed down, so that a building on which the non-combustible board has been constructed can be safely protected.

In addition, the present invention effectively blocks flames from being transferred to a non-combustible board, and since most of the components are inorganic raw materials, it is possible to obtain the effect of not generating toxic gases in the event of a fire.

Figures 2 to 6 are test results proving the non-combustibility of specimens manufactured according to the present invention.

Hereinafter, the results of a fire resistance test conducted by the Korea Construction & Living Environment Testing & Research Institute, a nationally accredited testing institute, on adhesive binder specimens manufactured according to the present invention using the examples of FIGS. 2 to 6 above will be described.

However, it is obvious to a person skilled in the art that these examples are only intended to more specifically explain the present invention and that the scope of the present invention is not limited by these examples.

Referring to Fig. 2, a non-flammability test and a gas toxicity test were conducted on the adhesive binder according to the present invention.

As a result of the non-combustibility test conducted three times, the ‘mass reduction rate’ for each test was within 11.7 to 12%, falling below the passing mark of 30%, and the ‘difference between the maximum temperature and the final equilibrium temperature’ was within 0.5 to 0.8 degrees, falling below the passing mark of 20 degrees.

In addition, the average behavioral stopping time of the test white rats was measured, and the results were 14 minutes and 45 seconds for test subject (specimen) 1 and 14 minutes and 4 seconds for test subject (specimen) 2, both exceeding the passing mark of 9 minutes.

Attached Figure 3 is a temperature change value graph of a non-flammability test, Figure 4 is the exhaust temperature and exhaust temperature curve results of a standard plate test, Figure 5 is the gas toxicity test result of test body 1, and Figure 6 is the gas toxicity test result of test body 2.

Through the above-described various fire resistance measurement tests, it was confirmed that the test specimens manufactured according to the present invention had test results that were suitable for the standards for fire resistance materials according to the Ministry of Land, Infrastructure and Transport notice.

Claims (3)

(a) a step of preparing a mixture by mixing at least one of liquid sodium silicate, liquid lithium silicate, potassium silicate, or colloidal silicate as a main component, and 60 to 75 wt% of the mixture based on 100 wt% of the high-temperature adhesive binder composition prepared through steps a to d below;
(b) a step of adding and mixing at least one of a silane coupling agent or an aluminate coupling agent in an amount of 0.5 to 2.5 wt% to the binder mixture of step a;
(c) a step of adding and mixing 15 to 30 wt% of at least one of kaolin, aluminum phosphide, zinc oxide, phosphorus oxide, metal oxide, expanded pearlite, expanded vermiculite, calcium carbonate, silicon dioxide, talc, and clay as a ceramic filler to the mixture of step b; and
(d) a step of adding and mixing 2 to 3 wt% of an acrylic resin emulsion and 1 to 5 wt% of an epoxy resin emulsion to the mixture of step c;
A method for manufacturing a ceramic high-temperature adhesive binder with enhanced adhesive strength. In paragraph 1,
When based on 100 wt% of the high-temperature adhesive binder composition manufactured through the above steps a to d below,
(e) a step of adding and mixing 1 to 3 wt% of zinc phosphate or red soil and then dispersing through a homogenizer;
A method for manufacturing a ceramic high-temperature adhesive binder with enhanced adhesive strength. Manufactured by one of the manufacturing methods of claim 1 or claim 2,
Ceramic high temperature adhesive binder with enhanced adhesive strength.