KR102285135B1 - Multi-functional environment-friendly organic-inorganic complex binder composition - Google Patents

Abstract

The present invention relates to an organic/inorganic composite binder composition including a liquid mixture containing PVA as a main ingredient and an inorganic solid powder phase containing calcium hydroxide as a main ingredient. According to the present invention, a functional inorganic material is added to PVA, which is a multi-functional water-soluble polymer, to form a composite, thereby providing a composite material which can be used as an eco-friendly organic/inorganic composite material realizing adhesiveness, waterproof property, flame resistance, antibacterial property, antifungal property and elasticity, and showing a significant decrease in emission of harmful substances and bad odor upon the fire accident. Therefore, the eco-friendly organic/inorganic composite material according to the present invention can be used as an eco-friendly waterproofing agent, eco-friendly paint and an industrial flooring material, in itself, and can be used as an adhesive or a binder with the other various materials to provide various types of heat insulation panels, buoys, or the like.

Description

Multifunctional organic-inorganic composite binder composition {MULTI-FUNCTIONAL ENVIRONMENT-FRIENDLY ORGANIC-INORGANIC COMPLEX BINDER COMPOSITION}

The present invention relates to a multifunctional organic-inorganic composite binder composition, and more particularly, by adding functional inorganic materials to an environmentally friendly water-soluble polymer polymer to form a composite material, adhesion, waterproofness, fire resistance, nonflammability, heat resistance, antibacterial properties, and antifungal properties , It relates to a multifunctional, environmentally friendly organic-inorganic composite binder capable of expressing mechanical elasticity.

Examples of ecological and environmental damage caused by the use of conventional organic synthetic resins based on petrochemicals are very diverse and can be directly found in the human habitation environment. In particular, for example, problems can be found in materials such as wallpaper, interior paints, preservatives, thermal insulation materials, and Styrofoam buoys.

Wallpaper or interior paint is a component of interior that can create interior beauty. Wallpaper today is composed of a variety of materials, such as laminated wallpaper coated with various materials, hemp wallpaper, PVC-based vinyl chloride wallpaper (aka silk wallpaper), and acrylic resin wallpaper. These wallpaper mixtures and adhesive raw materials are organic synthetic resins that emit various organic volatile substances such as formaldehyde. As wallpaper, the finishing material for interior walls, does not ventilate the room well, various organic volatile substances such as formaldehyde emitted from the wallpaper are the main culprit of sick house syndrome, raising social issues. In addition, all of the above wallpapers contain toxic substances such as toluene and styrene in pigments and paints for color, and vaporization of these components causes respiratory diseases and skin diseases. is becoming

In addition, paint, a paint used as a finishing material for interior walls, has its own chemical composition and emits a large amount of harmful substances. These paints are representative of water-based paints and oil-based paints, and each paint emits organic compounds such as benzene, toluene, xylene, and formaldehyde after painting. The paint that emits toxic substances in this way forms a film on the wall to protect the objects inside, and it cannot but be used.

Therefore, there is an urgent need to develop a new wallpaper or paint material that can finish the interior wall without releasing the harmful substances.

On the other hand, waterproofing materials are closely related to the living environment like wallpaper or paint. It is essential to the architectural civil engineering field and is directly related to the extension of the lifespan of the building structure. In general, when organic resins are used, except for sheet type, waterproofing effect is expected by mainly applying polyurethane or epoxy.

The problem with polyurethane waterproofing is that it cannot be applied in wet conditions. After at least 14 days have elapsed after rain, the moisture level of the surface to be coated must be less than 10% for construction to be possible.

On the other hand, although the coating film is not rubber, when exposed to sunlight, oxidation of the epoxy solid material remaining in the coating film proceeds quickly due to the rapid volatilization of the plasticizer that gives the flexibility of the epoxy. In addition, when applied to civil engineering fields where cement material is the main material, waterproofing is considered good at the beginning of construction, but since it is an organic rubber material that is different from the surface to be painted, the coefficient of expansion with the structure is different. There are disadvantages.

However, above all, it is very harmful to the human body due to the release of toxic volatile substances from polyurethane as it hardens during construction. In addition, if the coating surface is exposed to sunlight after use on the roof, corrosion occurs quickly, which causes the generation of microplastics. In addition, organic materials such as polyurethane or epoxy emulsion cannot expect antibacterial effects with a pH value of 4 or less, and have disadvantages in themselves that are very weak in environmental properties and flame retardancy.

In terms of overcoming these shortcomings of organic materials, inorganic silica penetration waterproofing materials have been developed and used in various forms. Silicate-based silica penetrates deep into concrete to make pores dense, maximizing the water-resistance and waterproofing effect, but it has a fatal flaw as a waterproofing agent that gradually leaches out of the remaining moisture in the concrete and loses its waterproofness. In addition, these silica-based waterproofing agents have good antibacterial properties with a pH value of 9 to 10, but have very weak thermal insulation properties and freeze-thaw properties. Therefore, it is required to develop organic/inorganic composite materials that can produce higher waterproofing efficiency in the waterproofing agent market and overcome the ecological and environmental disadvantages of organic materials.

Insulation insulation is also a material closely related to the living environment, like the wallpaper, paint, and waterproofing materials described above. Although it is not a fuel material that directly produces thermal energy necessary for living, it is a material that preserves thermal energy and has a function as a secondary energy source. The performance of the thermal insulation material is directly related to the thermal conductivity of the material. Thermal conductivity is based on the conduction electrons in the material. The intrinsic thermal conductivity of organic and inorganic materials is also determined by the average free path of conduction electrons in the material.

Based on this, from a macroscopic point of view of another heat transfer, gas is a good thermal insulation material because it has very low thermal conductivity when viewed as a material state. However, since the gas cannot maintain its special shape, it cannot be a thermal insulation material by itself, and the medium that traps the gas in an appropriate medium is used as an insulation material. Materials used as thermal insulation materials by trapping these gases are also divided into inorganic and organic types. They have pores inside the medium, and gas is contained in the pores. A representative material of the organic type is styrofoam or polyurethane foam, and the representative material of the inorganic type is foamed glass (or multifoam) or foamed glass bead. They each have intrinsic advantages and disadvantages as organic and inorganic thermal insulation materials. That is, foam glass or foamed glass beads, which are inorganic thermal insulation materials, are dimensionally stable thermal insulation insulation materials that do not burn at high temperatures due to their high heat resistance and fire resistance, but they cannot be compared with the excellent insulation performance of organic insulation materials.

Therefore, in Korea, relatively inexpensive organic materials such as styrofoam (polystyrene) and urethane foam are generally preferred as thermal insulation materials for residential use. However, heat resistance and fire resistance are relatively low, which is fatal in case of fire, and it becomes a very large fire, which causes material loss as well as toxic gas generated during combustion, which has fatal disadvantages that harm human life and health. For this reason, efforts are being made to increase the heat resistance and fire resistance of styrofoam or urethane foam, which are representative organic thermal insulation materials.

As an example, Korean Patent Registration No. 0602205 proposes a technique for improving the flame retardancy of Styrofoam beads by coating and crosslinking a mixture of expanded graphite, thermosetting liquid phenol resin and curing catalyst on polystyrene foam particles. However, there is a problem in that harmful gases are emitted during fuming because the phenol resin obtained by the condensation of phenol, which is harmful to the human body, and formaldehyde, which is a carcinogen, is used. There is a limit to the flame retardant treatment by such an organic resin, and there are also attempts to flame retardant through an inorganic material.

Korean Patent Laid-Open No. 10-2007-0121147 discloses a method for preparing a flame retardant composition in which an inorganic flame retardant, a silicate flame retardant, and various other inorganic fillers are combined to produce flame-retardant expanded polystyrene, and is mainly flame retardant using a liquid silicate compound. Try to maximize the effect. In this case, there is a problem in that the ratio of the inorganic material is too high, the loss of the inorganic material is excessively large, and the thermal insulation property of the organic insulation material is reduced. There is an urgent need to develop an environmentally friendly flame-retardant bonding material that can overcome these problems.

However, as an organic thermal insulation material, there is no such thing as 100% non-combustible material at a high temperature above a certain range. The solution is to use inorganic thermal insulation materials. In that respect, foamed glass or foamed glass beads are one of very good inorganic thermal insulation materials. Since the basic material is glass, it is undoubtedly a very good material as an insulator under high temperature conditions due to its high heat resistance and non-combustibility. In the case of bonding foamed glass particles or foamed glass beads, cement, which is a typical inorganic binder, can be used to make plates or bricks of a certain shape. However, in this case, the lightness, which is an important characteristic of foamed glass beads or foamed glass, is greatly lost due to the use of an inorganic binder called cement. When considering the use of other organic resin adhesives as a solution to this, the loss of lightness may not be large, but fire resistance is lost and even if it is made of a molded body, it becomes difficult to use it as a thermal insulation material at high temperature, which is its original purpose.

Therefore, for the wide use of foamed glass beads, which are good inorganic thermal insulation materials, an effective binder capable of forming a monolith as a uniform molded body is required.

Styrofoam buoys are a little far from ordinary living materials, but they are essential materials for fishermen's economic activities and aquaculture. But it is becoming a source of deadly garbage that makes the sea sick. Styrofoam buoys are easily broken into small pieces even with small impacts and corrosion. One Styrofoam buoy is split into about 7.5 million small grains, and in Korea, about 15 trillion grains are left in the sea, contributing to the generation of microplastics. Various methods have been proposed to solve this problem, but this solution also does not fundamentally deviate from the framework of organic plastics. To solve this problem, the use of inorganic materials such as soil composition is a long-term solution.

However, inorganic materials require a lot of energy because of the universality of inorganic materials having a high melting point to manufacture a molded article, and as a molded article such as plastic as a material, this elasticity is insufficient. In that respect, it would be an innovative solution to make the inorganic foam into a molded body using an eco-friendly organic binder, that is, to manufacture a buoy. The problem is an organic-inorganic composite agent having such functionality.

Korean Patent Registration 10-0602205 Korean Patent Publication 10-2007-0121147 Korean Public Utility Model 20-2014-0005973 Korean Patent Publication 10-2019-0050146 Korean Patent Laid-Open Patent No. 10-2019-0118935 Korean Patent Registration 10-1599258

Therefore, the present invention uses a functional water-soluble polymer that can overcome these disadvantages without using a resin that causes problems with the conventional organic resin-based binder, but mixes the water-soluble polymer with an inorganic material based on an alkaline earth metal material. An object of the present invention is to provide a multifunctional, environmentally friendly organic-inorganic composite binder composition.

In addition, the present invention also has an object to provide the use of the multifunctional, environmentally friendly organic-inorganic composite binder composition as a paint or waterproofing agent itself, or used as a various binder for molding with other components. .

Therefore, the organic-inorganic composite binder composition according to the present invention also has a purpose to provide a flame-retardant foamed Styrofoam panel, a non-flammable foamed glass bead panel, a sound absorbing body or a buoy.

The organic-inorganic composite binder composition according to the present invention is characterized in that it consists of a liquid mixture containing PVA as a main component and an inorganic solid powder form containing calcium hydroxide as a main component.

The liquid mixture containing PVA as a main component contains 5 to 65 parts by weight of PVA, 1 to 40 parts by weight of glycerin, 2 to 25 parts by weight of vegetable oil, 2 to 15 parts by weight of ethyl alcohol, and 2 to 9 parts by weight of calcium chloride based on 100 parts by weight of water. is made up of parts by weight,

The inorganic solid powder having the calcium hydroxide as a main component is 5 to 40 parts by weight of calcium hydroxide, 1 to 25 parts by weight of magnesium hydroxide, 1 to 8 parts by weight of aluminum hydroxide, and 1 to zinc oxide based on 100 parts by weight of water contained in the liquid mixture. It is preferably composed of ~ 5 parts by weight.

According to an embodiment of the present invention, the organic-inorganic composite binder composition has a liquid mixture containing PVA as a main component as one component, and an inorganic solid powder containing calcium hydroxide as a main component as two components to be used as an adhesive. there is.

According to an embodiment of the present invention, the organic-inorganic composite binder composition may be used as a binder to express waterproofness, fire resistance, nonflammability, antibacterial property, antifungal property, heat insulation property, and elasticity.

According to an embodiment of the present invention, the organic-inorganic composite binder composition may be used as a waterproofing agent or a paint agent by simply mixing a liquid mixture containing PVA as a main component and an inorganic solid powder phase containing the calcium hydroxide as a main component.

According to an embodiment of the present invention, the waterproofing agent may be an eco-friendly elastic coating waterproofing agent.

According to an embodiment of the present invention, a flame-retardant foamed styrofoam panel is provided by using the organic-inorganic composite binder composition as a binder for foamed styrofoam.

According to an embodiment of the present invention, a non-combustible foamed glass bead panel, sound absorbing body or buoy is provided by using the organic-inorganic composite binder composition as a binder for foamed glass beads.

According to the present invention, adhesion, waterproofness, fire resistance, antibacterial properties, antifungal properties, and elasticity are expressed by adding functional inorganic substances to PVA, a water-soluble polymer with multi-functionality, and forming a composite material. It is possible to prepare a composite agent that can be used as an environmentally friendly organic-inorganic composite material that is significantly degraded.

Therefore, the environment-friendly organic-inorganic composite agent according to the present invention can be used not only as an eco-friendly waterproofing agent, eco-friendly paint, and industrial flooring agent, but also as an adhesive or binder with various other materials, so that it can be used as various types of insulation panels or buoys. Applicable.

1 is a photograph confirming the presence or absence of wallpaper formation of wallpaper paint prepared in Example 1;
Figure 2 is the result of confirming the applicability of the wallpaper paint prepared in Example 1 after painting the cement substrate (left) and the plastic shape (right),
3 is a photograph confirming the waterproofness and water repellency of the wallpaper paint prepared in Example 1;
4 and 5 are photographs confirming the effect of erasing graffiti using the water-based pen 4 and the oil-based magic 5 of the wallpaper paint prepared according to Example 1;
6 is a result of confirming the antibacterial and antifungal properties of the wallpaper paint prepared in Example 1 and the comparative wallpaper paint;
7 is a result of confirming the waterproofness of the elastic coating waterproofing agent prepared according to Example 2;
8 is a result of confirming the elasticity of the elastic coating waterproofing agent prepared according to Example 2;
9 is a non-flammability confirmation result of the styrofoam insulation panel manufactured according to Example 3;
10 is a light weight and waterproof test result of the styrofoam insulation panel manufactured according to Example 3;
11 is a form of a foamed glass bead panel prepared using a composite binder prepared with a composition according to Example 4;
12 is a result of confirming the non-combustibility of the foamed glass bead panel prepared according to Example 4,
13 to 15 are photographs of buoys prepared based on foamed glass beads each prepared according to Examples 5 to 7 and the results of confirming the buoyancy while maintaining them in water for 30 days or more.

Hereinafter, the present invention will be described in more detail as follows.

The terminology used herein is used to describe specific embodiments, not to limit the present invention.

As used herein, the singular forms may include the plural forms unless the context clearly dictates otherwise. Also, as used herein, “comprise” and/or “comprising” refers to the presence of the recited shapes, numbers, steps, actions, members, elements, and/or groups of those specified. and does not exclude the presence or addition of one or more other shapes, numbers, movements, members, elements and/or groups.

The present invention relates to an organic-inorganic composite binder composition comprising a liquid mixture containing PVA as a main component and an inorganic solid powder containing calcium hydroxide as a main component, and a method for utilizing the same for various purposes.

'Organic-inorganic composite binder' used throughout the specification of the present invention means a composite binder in which an organic component containing PVA as a main component and an inorganic component containing calcium hydroxide as a main component are mixed, wherein the binder is a third other component. , for example, is meant to include things that act as an adhesive for bonding Styrofoam, Styrofoam foam, foam glass beads, etc. or a molding agent that can be molded.

In addition, the meaning of the main component in 'PVA as a main component' and 'Calcium hydroxide as a main component' means having the largest content range among each composition.

Therefore, the organic-inorganic composite binder composition according to the present invention is a mixture of a liquid mixture containing PVA as a main component and an inorganic solid powder phase containing calcium hydroxide as a main component. It can also be used as a molding binder of the component.

The liquid mixture containing the PVA as a main component included in the organic-inorganic composite binder composition according to the present invention is 5 to 65 parts by weight of PVA, 1 to 40 parts by weight of glycerin, and 2 to 25 parts by weight of vegetable oil based on 100 parts by weight of water. , preferably composed of 2 to 15 parts by weight of ethyl alcohol and 2 to 9 parts by weight of calcium chloride.

In the present invention, candidate materials were selected according to the following criteria to select eco-friendly, water-soluble polymers as materials that can solve problems caused by environmental hormone emission problems of conventional organic resins.

go. The water-soluble polymer polymer structure is a material composed of carbon, hydrogen, and oxygen. When burned, it decomposes into water and carbon dioxide, so that harmful volatile substances are not generated, and it must be capable of ensuring safety against harmful gases.

me. When dispersed in water, micropores are formed and it has a high specific surface area and has excellent moisture absorption. It has humidity control, soundproofing and deodorizing functions, and reacts with heavy metal ions to insolubilize harmful heavy metals, lead cadmium, mercury, hexavalent chromium, etc. It should be a polymer resin that is safe from harmful heavy metals by adsorbing, insoluble, and solidifying it.

all. It has low thermal conductivity, thermal insulation properties, and a stable crystal structure to prevent shrinkage and deformation of Pyeongchang due to moisture. Also, since there is an alcohol group in the molecule, it does not cause molecular cleavage, so it must be a durable polymer with excellent resistance to UV rays.

La. Organic resin that does not generate volatile aromatic hydrocarbons (VACs) such as toluene, xylene, and ethylbenzene as binders, does not contain harmful solvents such as methanol and methyl ethyl ketone, and does not contain or generate harmful chemicals such as carcinogen formaldehyde must be material.

According to these selection criteria, in the present invention, polyvinyl alcohol (PVA) was selected as a water-soluble polymer capable of imparting adhesion, elasticity, and ecological functions.

The PVA is a water-soluble material consisting of carbon, hydrogen, and oxygen having a hydroxyl group, and has antibacterial properties due to a hydroxyl group (OH-) group without nitrogen oil or chlorine component, and the flexible film film also has an insulating effect. In addition, since it is biodegradable by microorganisms, it is composed of eco-friendly and eco-friendly water-soluble polymers to solve environmental problems.

Therefore, PVA is a porous material. It is a water-soluble material with excellent humidity control function, non-combustibility, thermal insulation, antibacterial, soundproofing, anti-fouling and deodorizing function, sound insulation function, heat insulation function, flame retardant function, heavy metal adsorption function, adhesion and emulsification. Since it is a material, it is a material suitable for achieving the object of the present invention.

It is appropriate that the PVA is contained in an amount of 5 to 65 parts by weight based on 100 parts by weight of water. If the PVA content is less than 5 parts by weight, it is difficult to obtain the desired physical properties due to poor flexibility and bonding strength. However, when particularly high elasticity is required, up to 70 parts by weight can be used.

In addition, in the liquid mixture containing PVA as a main component, 1 to 40 parts by weight of glycerin, 2 to 25 parts by weight of vegetable oil, 2 to 15 parts by weight of ethyl alcohol, and 2 to 9 parts by weight of calcium chloride based on 100 parts by weight of water. .

The glycerin (Glycerin) is added to prevent freeze-thaw, pigment dispersion and adhesion enhancer, especially to maintain elasticity of the organic-inorganic composite binder. In addition, when the organic-inorganic composite binder of the present invention is used as a wallpaper paint by forming a network structure with PVA, the effect of enhancing the moisture-resistance function of the coating film is expressed. The added amount is preferably 1 to 40 parts by weight based on 100 parts by weight of water. When the amount added is less than 1.0, the dispersibility of the pigment is poor during the paint painting operation, there is no effect of preventing freeze-thaw, and when the amount exceeds 40 parts by weight, it is difficult to maintain the viscosity of the paint.

The vegetable oil (oil) is a component that imparts the fluidity and mechanical elasticity of the organic-inorganic composite binder, for example, edible oil, olive oil, perilla oil, sesame oil, palm oil, corn oil, etc., but the type is not limited and can be used. there is. 2 to 25 parts by weight of the vegetable oil is appropriate based on 100 parts by weight of water, and when it exceeds 25 parts by weight, curing is delayed and flame retardancy becomes a problem, which can cause soot. is lowered

The ethyl alcohol (ethanol) is used to impart dispersion, catalytic function, defoaming function, and mixture crystal prevention function of the inorganic solid powder containing calcium hydroxide as a main component in the composition of the present invention. In the present invention, it is preferable to add ethanol to a liquid mixed solution containing PVA as a main component so that it can be stably maintained in the liquid phase, and 2 to 15 parts by weight is appropriate with respect to 100 parts by weight of water. When the amount added is less than 2 parts by weight, the function expression is insufficient, and in particular, the defoaming property is poor.

In addition, the calcium chloride (CaCl ₂ ) has a combustion gas generation suppression and deodorizing function during combustion, and the amount added is appropriate 2 to 9 parts by weight based on 100 parts by weight of water. If the calcium chloride (CaCl ₂ ) exceeds 9 parts by weight, curing may be delayed, the mixability of the mixture may be deteriorated, and corrosion of the structure may result. there is.

The liquid mixture containing PVA as a main component according to the present invention having the above composition is first maintained at 70° C. to 80° C. of water, and PVA powder is slowly added to the content range and dissolved to prepare a PVA water-soluble polymer solution. Here, glycerin, vegetable oil, ethyl alcohol and calcium chloride in each content range are added and mixed sufficiently to prepare the main composition.

In addition, the inorganic solid powder containing calcium hydroxide as a main component included in the organic-inorganic composite binder composition of the present invention is 5 to 40 parts by weight of calcium hydroxide, 1 to 25 parts by weight of magnesium hydroxide, based on 100 parts by weight of water contained in the liquid mixture. , 1 to 8 parts by weight of aluminum hydroxide, and 1 to 5 parts by weight of zinc oxide.

The inorganic solid powder phase containing the calcium hydroxide as a main component hardens PVA in the liquid mixture based on the PVA, and combines PVA and an inorganic ceramic material that is compatible with PVA, which can exhibit various functions that can compensate for the disadvantages of PVA resin. is constituted by

Specifically, it is a curing agent for PVA resin and contains calcium hydroxide as a main component to impart antibacterial and antifungal properties by controlling acidity. The calcium hydroxide is a component that strongly inhibits the growth of bacteria or fungi by imparting alkalinity in an aqueous solution. The amount of calcium hydroxide added is 5 to 40 parts by weight based on 100 parts by weight of water contained in the liquid mixture containing PVA as a main component. In this case, it is preferable to use within the above range because hardening comes quickly and the surface is not smooth during construction.

In addition, when the organic-inorganic composite binder composition of the present invention is applied to indoor wallpaper or paint by itself, it is very important to control the particle size. In general, a particle size of -200 mesh can be used, but in case of application or use for paints such as wallpaper paint and ceramic paint, the particle size of the calcium hydroxide is preferably particles (-325 mesh) that have passed through a 325 mesh sieve.

The magnesium hydroxide Mg(OH) ₂ is an additional curing agent, and is added to give an antioxidant function, an increase in durability, an antibacterial function, and a flame retardant function, and it is appropriate to add 1 to 25 parts by weight based on 100 parts by weight of water. When the amount added is less than 1 part by weight, the flame retardancy is lowered, and when added in excess of 25 parts by weight, the viscosity of the organic-inorganic composite binder is increased, so it is not appropriate, so it is preferable to use it within the above range.

In addition, the aluminum hydroxide Al(OH) ₃ imparts durability, corrosion prevention, combustion prevention and flame retardancy, and durability is important when the organic-inorganic composite binder composition of the present invention is used as a wallpaper paint or wall waterproofing agent. Characteristically, Al(OH) ₃ is hydrophobic and has a low water absorption coefficient, so it is appropriate to add 1 to 8 parts by weight based on 100 parts by weight of water. When added in an amount of less than 1 part by weight, it is difficult to maintain characteristics such as durability, and when it exceeds 8 parts by weight, solubility of inorganic substances is poor, and ecology, humidity control function, and antibacterial properties may be reduced, so it is preferable to use within the above range.

The zinc oxide ZnO may be added for the purpose of reinforcing antibacterial activity as an antibacterial agent and has the effect of blocking ultraviolet rays. Therefore, when the composition of the organic-inorganic composite binder of the present invention is used as a waterproofing agent for an elastic coating film, waterproofing a roof, or as a binder for a buoy, it is particularly important to provide a UV protection function. It is appropriate to add 1 to 5 parts by weight based on 100 parts by weight of water. Addition of less than 1 part by weight is difficult to expect a function, and when it exceeds 5 parts by weight, it is not easy to coat the binder.

The inorganic solid powder phase containing calcium hydroxide as a main component is a solid powder phase that acts as a curing agent when calcium hydroxide, magnesium hydroxide, aluminum hydroxide, and zinc oxide having each content range are added step by step so as to be uniformly mixed, and then thoroughly mixed and stirred for 20 to 30 minutes Mixtures can be prepared.

In the present invention, without adding additional components in addition to the composition of the organic-inorganic composite binder presented above, when used within the composition range of the indicated components, it is used as it is in the indoor wallpaper or paint presented in the present invention through a slight quantitative adjustment; It can be used for various types of molding binders, such as waterproofing agents, thermal insulation materials, or buoys, and exhibits the intended performance. However, it is not a key composition for the efficiency or productivity of the process for the intended purpose, but a separate component may be optionally added.

In addition, the organic-inorganic composite binder composition according to an embodiment of the present invention has a liquid mixture containing PVA as a main component as one component, and an inorganic solid powder containing calcium hydroxide as a main component as two components. It can be used as an adhesive. there is.

In addition, the organic-inorganic composite binder composition according to an embodiment of the present invention may be used as a binder to express waterproofness, fire resistance, nonflammability, antibacterial properties, antifungal properties, heat insulation properties, and elasticity.

In addition, the organic-inorganic composite binder composition according to an embodiment of the present invention may be used as a waterproofing agent or paint agent by simply mixing a liquid mixture containing PVA as a main component and an inorganic solid powder phase containing the calcium hydroxide as a main component.

In addition, according to an embodiment of the present invention, the waterproofing agent may be an eco-friendly elastic coating waterproofing agent. In the case of such an elastic coating waterproofing agent, it may be manufactured for the purpose of using an existing polyurethane waterproofing agent as a waterproofing agent for a floor or a roof.

In addition, the organic-inorganic composite binder composition according to the present invention can be applied to a flame-retardant foamed Styrofoam panel by using it as a binder for foamed Styrofoam.

In addition, according to an embodiment of the present invention, the organic-inorganic composite binder composition can be used as a binder for foamed glass beads and can be applied as a non-combustible foamed glass bead panel, sound absorbing body or buoy.

When preparing the non-flammable foamed glass beads, it is also preferable to implement various colors by adding an appropriate amount of pigment.

However, it is apparent to those skilled in the art that the organic-inorganic composite binder composition according to the present invention can be used for various purposes other than the above application examples.

Hereinafter, preferred embodiments of the present invention will be described in detail. The following examples are only for illustrating the present invention, and the scope of the present invention should not be construed as being limited by these examples. In addition, although specific compounds are used for illustration in the following examples, it is apparent to those skilled in the art that similar effects can be exerted even when equivalents thereof are used.

Example 1: Preparation of wallpaper paint for indoor use

A PVA aqueous solution was prepared by slowly adding 12 parts by weight of PVA powder to 100 parts by weight of water while maintaining the water temperature at 70° C. to 80° C. and dissolving it. 6 parts by weight of glycerin, 4 parts by weight of vegetable olive oil, 4 parts by weight of ethyl alcohol, and 3 parts by weight of calcium chloride were added to the PVA aqueous solution and thoroughly mixed to prepare a main composition.

Then, based on 100 parts by weight of water in the main composition, 15 parts by weight of calcium hydroxide (particles passing through a 325 mesh sieve (-325 mesh)) as a second component made of a functional inorganic material, 5 parts by weight of magnesium hydroxide, 2 parts by weight of aluminum hydroxide, and oxide After adding 1 part by weight of zinc stepwise, the mixture was thoroughly mixed and stirred for 20 to 30 minutes to prepare a hardener composition in a solid powder mixture.

The interior wallpaper paint was prepared by mixing the main composition and the curing agent composition and kneading the resulting sludge mixture for 2-3 minutes.

Experimental Example 1: Confirmation of curing conditions

After the wallpaper paint prepared according to Example 1 was painted on various substrates, physical properties such as curing conditions, water repellency, graffiti erasing function, antifungal mold, and sick house syndrome removal function were investigated.

First, in order to check the curing conditions, the curing temperature was changed to 5°C, 20°C, and 30°C as shown in Table 1 below to allow complete curing. As shown in Table 1 below, it was confirmed that complete curing was achieved in 2 hours at room temperature, and complete curing was possible in 1 hour in an atmosphere of 30°C.

division 5℃/hour 20℃/hour 30℃/hour touch One 0.7 0.5 fully cured 4 2 One repaint 5 3 2

Experimental Example 2: Confirmation of indoor wallpaper formation

By applying the wallpaper paint prepared in Example 1 to the glass surface, it was visually confirmed whether it was formed in the form of a film to act as an indoor wallpaper, and the results are shown in FIG. 1 below.

Next, referring to FIG. 1 , it can be seen that the film is formed in the form of a film to the extent that it can act as a complete wallpaper.

Experimental Example 3: Confirmation of applicability of wallpaper paint

In order to check whether the wallpaper paint prepared in Example 1 is effectively painted on various materials, it was painted on a round cement substrate (left) and square-shaped plastic (right) having a certain thickness, and then the applicability was visually observed. was confirmed, and the results are shown in FIG. 2 below.

Next, referring to FIG. 2, it was confirmed that the shape was painted on a cement substrate (left), plastic shape (right), etc., and a homogeneous wall surface was formed.

Experimental Example 4: Confirmation of waterproofness and water repellency of wallpaper paint

After the wallpaper paint of Example 1 was applied to a plastic substrate of a certain size and completely cured, the wallpaper paint was tested for waterproofing and water repellency, and the results are shown in FIG. 3 below.

Referring to FIG. 3 below, it can be seen that a perfect waterproof state is maintained in which water droplets are not absorbed even when water is dropped after the wallpaper paint is painted.

Experimental Example 5: Confirmation of graffiti erasing effect of wallpaper paint

In order to check whether the wallpaper paint prepared according to Example 1 has the effect of erasing graffiti, it was applied to a plastic substrate of a certain size as in Example 4, cured completely, and then graffitied with a water-based pen and oil-based magic. After leaving for 24 hours, the graffiti was completely stabilized, and the change after erasing with a towel soaked in water was visually confirmed, and the results are shown in FIGS. 4 and 5 below.

Next, referring to FIGS. 4 and 5 , it was confirmed that both the water-based pen ( FIG. 4 ) and the oil-based magic (5) were clearly erased without traces of the scribbled sign pen and the magic pen. Although the above experiment was the result after leaving it for 24 hours, the same result was shown even after 7 days.

Experimental Example 6: Confirmation of antibacterial and antifungal properties

The antibacterial properties of the wallpaper paint prepared in Example 1 were confirmed through comparative experiments by purchasing any commercially available paint. This antimicrobial confirmation test was conducted according to the Halo Test (ASTM G-21), and Aspergillus niger KCTC 6986 was used as the test strain. First, the primary cultured fungal bacteria were inoculated on 5 mm x 5 mm wallpaper coated with Example 1 and comparative wallpaper paint, and after 24 hours incubation in an incubator, mold inhibitory power was confirmed for 4 weeks, and comparison shots were taken every week. . The reading method for these results was carried out according to the anti-fungal test result reading method ^* , which is an official verification, and the results are shown in FIG. 6 and Table 2 below.

Next, referring to FIG. 6 , in the case of the comparative wallpaper paint, a little mold started to grow only on the edge after one week, but after two weeks, the mold grew on more than 60% of the wallpaper, and the anti-fungal reading method No. 4 was read. Results came out, and over time, almost 100% of the surface had mold growth.

However, in the case of the wallpaper paint prepared in Example 1 of the present invention, there was no trace of growth of black mold. From these results, it was confirmed that the wallpaper paint composition according to the present invention had excellent airfoil performance.

In addition, the results of the extended antimicrobial test conducted above 4 weeks to 15 weeks are shown in Table 2 below. As shown in Table 2, in the case of the comparative wallpaper paint, as confirmed in Photo 6, after 2 weeks, the wallpaper grew to 60% or more, and the antifungal reading method No. Mold has grown on the surface. Relatively, it was confirmed that the growth of black mold was almost suppressed up to 15 weeks in all of the wallpaper paints prepared in Example. In conclusion, it was confirmed that the wallpaper paint prepared with the organic-inorganic composite binder composition presented in the present invention exhibited excellent antibacterial and antifungal properties.

Sample classification Rating 1 week 5 weeks 10 week 15 weeks Commercial Comparison Paint One 4 4 4 Example 1 0 0 0 One

*Anti-fungal test reading method; Evaluation index readout criteria: 0 = No growth of mold was observed in the sample, 1 = Growth of mold was less than 10% in the sample, 2 = Growth of mold was more than 10% to less than 30% in the sample, 3 = There was more than 30% to less than 60% of mold growth in the sample, 4 = more than 60% mold growth in the sample.

Example 2: Preparation of the composition of the elastic coating film waterproofing agent of the floor and the roof

A PVA aqueous solution was prepared by slowly adding 60 parts by weight of PVA powder to 100 parts by weight of water while maintaining the water temperature at 70° C. to 90° C. and dissolving it. 35 parts by weight of glycerin, 23 parts by weight of vegetable oil, 4 parts by weight of ethyl alcohol, and 5 parts by weight of calcium chloride were added to the PVA aqueous solution and thoroughly mixed to prepare a main composition.

Then, 38 parts by weight of calcium hydroxide, 4 parts by weight of magnesium hydroxide, 5.5 parts by weight of aluminum hydroxide, and 2.0 parts by weight of zinc oxide are added in stages based on 100 parts by weight of water contained in the main composition, and then mixed and stirred sufficiently for 20 to 30 minutes to prepare a curing agent composition was prepared.

An elastic coating waterproofing agent was prepared by mixing the main composition and the curing agent composition and kneading the resulting sludge mixture for 2-3 minutes.

Experimental Example 7: Confirmation of construction process and physical properties of elastic coating film

The construction process was confirmed by comparing the waterproofing agent for the elastic coating film according to Example 2 of the present invention with the commonly used urethane waterproofing method.

The urethane waterproofing method is very complicated as it has to go through 3 processes of bottom coating, middle coating, and top coating.

However, the elastic coating waterproofing agent prepared according to Example 2 of the present invention was not only completed in the first step process, but also could be applied when the moisture of the base surface was 80% or more, and no lifting phenomenon was observed.

In addition, urethane construction has a disadvantage in that the drying time after construction is at least 48 hours on average, and the construction period is long, resulting in a lot of waste of time. However, it was confirmed that the elastic coating waterproofing agent composed of the composition of the present invention was cured within 12 hours.

The physical properties of the elastic coating waterproofing agent made of the composition of the present invention through the above process were measured as follows.

1) Finish - matte or semi-gloss

2) Dry film thickness - 2~3 times thickness 1.5~2mm

3) Application amount - It varies depending on the substrate, but on average 2kg/㎡ (2mm thickness)

4) Hardness - 80 or more (urethane 5 to 60)

5) Elongation - over 350

6) Tensile strength - 3N/㎟ or more

7) Dilution and cleaning agent - water (urethane thinner is used for urethane)

8) Repainting - possible after 12 hours (after 48 hours of urethane)

Experimental Example 8: Confirmation of waterproofness of the elastic coating film

The waterproofness of the elastic coating waterproofing agent prepared according to Example 2 was confirmed by immersing it in water for at least 30 days after coating the coating on the cement block substrate, and the results are shown in FIG. 7 below.

Next, referring to FIG. 7 , it was confirmed that the coating film immersed in water for 30 days or more did not swell or show any peeling phenomenon. From these results, it was confirmed that the charcoal manufactured according to the present invention can be effectively applied as a waterproofing agent for floors or roofs by having excellent waterproofing properties.

Experimental Example 9: Confirmation of elasticity of elastic coating film

After applying the elastic coating waterproofing agent prepared according to Example 2 to the glass surface, it was dried to check whether or not there was elasticity, and the results are shown in FIG. 8 below.

Next, referring to FIG. 8 , it can be seen that the elastic coating film has elasticity and elasticity like rubber. Therefore, it was confirmed that the elastic coating film according to the present invention is an alternative that can effectively replace the existing urethane coating film.

Example 3: Application as a molding binder in the manufacture of flame-retardant Styrofoam panels

1) Manufacture of flame retardant flame retardant styrofoam panel

For the waste Styrofoam, the size of the Styrofoam beads crushed by the crusher was extracted to a particle size of 3mm to 5mm and used. Alternatively, you may purchase commercially available Styrofoam beads and use them.

2) Manufacture of molding binder: preparation of main material and curing agent

PVA aqueous solution was prepared by slowly adding 11 parts by weight of PVA powder to 100 parts by weight of water while maintaining the water temperature at 70° C. to 80° C. and dissolving it. A main composition was prepared by adding 16 parts by weight of glycerin, 6 parts by weight of ethanol, 10 parts by weight of vegetable olive oil, and 4 parts by weight of calcium chloride to the PVA aqueous solution.

Then, 11 parts by weight of calcium hydroxide, 9 parts by weight of magnesium hydroxide, 2 parts by weight of ZnO, and 4 parts by weight of aluminum hydroxide based on 100 parts by weight of water contained in the main composition were taken and mixed well to prepare a curing agent solid powder composition.

3) Manufacture of flame-retardant Styrofoam insulation panel

In 1), the Styrofoam beads having a size of 3 mm to 5 mm are transferred to the mixing mixer and the weight ratio is calculated at the same time, and the main composition prepared in 2) and the solid powder curing agent composition are put in, the Styrofoam beads are 100 parts by weight of water in the main composition Pour into a mixer so that it becomes 10 parts by weight, knead for 5-10 minutes, then discharge into a mold with dimensions of 150 mm in width, 100 mm in length, and 30 mm in width, and then chop well with a spoon and place well. After 4 hours at 25 ℃ room temperature, through the demolding process to obtain a flame-retardant styrofoam insulation panel.

As a result of confirming the final dry state of the Styrofoam insulation panel manufactured according to the above process, the total weight was 50 g, which was found to be almost identical to 0.1 g/cm 3 , which is the specific gravity of the non-combustible material that can satisfy the lightness of the insulation.

That is, as a result of applying the organic-inorganic composite composite prepared with the composition of Example 3 of the present invention to Styrofoam beads, a molded body was formed in a very stable form, and it was confirmed that the organic-inorganic composite composite was used as an effective binder.

Experimental Example 10: Non-combustibility test of Styrofoam insulation panel

In order to confirm the non-combustibility of the styrofoam insulating panel manufactured according to Example 3, a torch flame test was performed with the molded body of the styrofoam insulating panel maintained at a distance of 25 cm, and the results are shown in FIG. 9 below. .

As can be seen in FIG. 9 , the molded body of the manufactured Styrofoam insulation panel did not burn or deform the molded body even after a non-combustible test for 3 minutes with a torch flame test. Its state shows the possibility that it can be used as a flame-retardant Styrofoam panel having a thermal insulation function corresponding to the minimum flame-retardant class 3.

Experimental Example 11: Light weight and waterproof test of Styrofoam insulation panel

The Styrofoam insulation panel prepared according to Example 3 was placed in water and left for at least 30 days to see lightness and waterproofness, and the shape change was visually confirmed, and the results are shown in FIG. 10 .

Next, referring to FIG. 10, it was confirmed that the molded Styrofoam manufactured according to the present invention maintained a very stable shape for more than 30 days. It can be confirmed that the composite binder prepared with the composition of Example 3 is a molding binder that imparts thermal stability, fire resistance and waterproof properties.

Example 4: Application as a molding binder in the manufacture of foamed glass bead panels

1) Preparation of foamed glass beads

Commercially available foamed glass beads can be purchased and used, but in order to make a molded body as follows, foamed glass beads were prepared and used as raw materials.

(1) finely pulverizing the waste glass to a size of 63 μm or less in average diameter;

(2) mixing a molding binder, a foaming agent, and a pore control additive with the pulverized glass powder to prepare a raw glass for manufacturing foamed glass beads;

(3) supplying water enough to be kneaded to the raw glass for manufacturing the foamed glass beads and granulating the glass powder into a spherical molded body in a disk-shaped molding machine;

(4) drying and preheating the spherical shaped body in a rotary kiln;

(5) introducing the preheated spherical molded body and the solid powder having a high melting point of 1000°C or higher as a mold release agent together into a rotary kiln controlled at 780 ~ 900°C, followed by foaming and firing;

(6) stabilizing the foamed glass beads by introducing them at 500 to 600° C.

(7) removing the thermal stress generated during foaming by annealing the stabilized foamed glass beads to 40° C. and preparing foamed glass beads;

(8) The foamed glass beads were prepared through the steps of preparing foamed glass beads having an average diameter of 1 to 4 mm by sieving the foamed glass beads from which the thermal stress was removed. The density of the thus prepared foamed glass beads is in the range of 0.35 to 0.5 g/cm 3 on average.

2) Manufacture of molding binder: preparation of main material and curing agent

A PVA aqueous solution was prepared by slowly adding and dissolving 17 parts by weight of PVA powder while maintaining the water temperature at 70° C. to 90° C. in 100 parts by weight of water. A main composition was prepared by adding 16 parts by weight of glycerin, 7 parts by weight of ethanol, 14 parts by weight of vegetable olive oil, and 5 parts by weight of calcium chloride to the PVA aqueous solution.

Then, based on 100 parts by weight of water contained in the main composition, 16 parts by weight of calcium hydroxide, 23 parts by weight of magnesium hydroxide, 2 parts by weight of zinc oxide, and 5 parts by weight of aluminum hydroxide were taken and mixed to prepare a curing agent composition.

3) Manufacture of foamed glass bead panel

With respect to 100 parts by weight of water contained in the subject matter, 560 parts by weight of foamed glass beads having a size of 1 to 4 mm were added to the molding binder prepared in 2) and mixed for 5 to 10 minutes so that they could be well coated on the surface of the foamed glass beads. Then, it was put in a mold having a size of 150 mm in width, 100 mm in length, and 30 mm in height, minced well, dried for about 4 hours, and then demolded to prepare a foamed glass bead panel.

Experimental Example 12: Confirmation of the shape of the foamed glass bead panel

The shape of the foamed glass bead panel prepared using the composite binder prepared with the composition according to Example 4 is shown in FIG. 11 below.

As shown in the photo of FIG. 11 , it can be seen that the foamed glass beads having an average diameter of 1 to 4 mm are well combined to maintain the panel shape. It can be seen that the composite binder according to Example 4 of the present invention was properly applied as a molding binder for foamed glass beads.

Experimental Example 13: Confirmation of non-combustibility of foamed glass bead panel

In order to confirm the non-combustibility of the foamed glass bead panel prepared according to Example 4, a torch flame test was performed so that the flame could be forcibly burned while maintaining the state in which the torch flame was in direct contact with the surface of the molded body of the foamed glass bead panel prepared according to Example 4 was carried out, and the results are shown in FIG. 12 below.

As can be seen in FIG. 12 , the molded body of the manufactured foamed glass bead panel was burnt slightly black in the molded body directly in contact with the flame even after a non-combustible test for 3 minutes with a torch flame test, and combustion occurred in the molded body itself or No deformation of the molded body itself occurred. In the case of commercially available flame torches, there are differences for each product, but according to the specifications of the product, the temperature of the torch flame is at least 1000 ° C. is judged Nevertheless, the results of these torch flame experiments confirmed that the performance of the foamed glass bead panel molded with the organic-inorganic composite binder of the present invention can be used as a panel having a thermal insulation function corresponding to a non-flammable material.

Examples 5-7: Application as a molding binder in the manufacture of buoys using foamed glass beads

1) Manufacturing of molding binder: preparation of main material and curing agent

A PVA aqueous solution was prepared by slowly adding 20 parts by weight of PVA powder while maintaining the water temperature at 70° C. to 90° C. in 100 parts by weight of water. A main composition was prepared by adding 16 parts by weight of glycerin, 7 parts by weight of ethanol, 15 parts by weight of vegetable olive oil, and 3 parts by weight of calcium chloride to the PVA aqueous solution.

Then, based on 100 parts by weight of water in the main composition, 16 parts by weight of calcium hydroxide, 5 parts by weight of magnesium hydroxide, 4 parts by weight of zinc oxide, and 3 parts by weight of aluminum hydroxide were respectively taken and mixed to prepare a curing agent composition.

In Examples 6 and 7, the remaining compositions were applied in the same manner, except for preparing by adding 0.01 parts by weight of each of yellow and red pigments in the curing agent composition.

2) Manufacturing of buoys based on foamed glass beads

Mix both the main agent and the curing agent composition to make them uniform, and then add 140 to 150 parts by weight (7 to 8 cups of paper cups) with respect to 100 parts by weight of water contained in the main composition of 3 mm to 5 mm foamed glass beads. After mixing for 5 to 10 minutes so as to be well coated on the surface of the beads, they were put in molds of various sizes and shapes, minced well, dried for about 4 hours, and demolded to prepare a foamed glass bead-based buoy.

Experimental Example 14: Confirmation of buoyancy of foamed glass bead buoy

The photos of the buoys prepared based on the foamed glass beads prepared according to Examples 5 to 7 and their buoyancy were checked while maintaining them in water for at least 30 days, and the results are shown in FIGS. 13 to 15, respectively.

Referring to this, it can be seen that all the buoys are stably maintained buoyancy for more than 30 days regardless of the pigment addition, and in particular, as in FIG. Announcement glass buoy according to Example 5 can be confirmed that the buoyancy is maintained.

Therefore, the organic-inorganic composite binder presented in the present invention effectively acts as a molding binder for foamed glass beads, and in particular, a molded article with enhanced water resistance can be used in the manufacture of buoys.

Claims (8)

A liquid mixture consisting of 5 to 65 parts by weight of PVA, 1 to 40 parts by weight of glycerin, 2 to 25 parts by weight of vegetable oil, 2 to 15 parts by weight of ethyl alcohol, and 2 to 9 parts by weight of calcium chloride based on 100 parts by weight of water;
9 to 40 parts by weight of calcium hydroxide, 1 to 25 parts by weight of magnesium hydroxide, 1 to 8 parts by weight of aluminum hydroxide, and 1 to 5 parts by weight of zinc oxide based on 100 parts by weight of water contained in the liquid mixture. Organic-inorganic composite binder composition, characterized in that. delete The method of claim 1,
The organic-inorganic composite binder composition includes the liquid mixture as one component and the inorganic solid powder as two components to be used as an adhesive. The method of claim 1,
The organic-inorganic composite binder composition is an organic-inorganic composite binder composition that is used as a binder to express waterproof, fire resistance, non-flammability, antibacterial, antifungal, thermal insulation, and elasticity. The method of claim 1,
The organic-inorganic composite binder composition is an organic-inorganic composite binder composition that is used as a waterproofing agent or a paint agent by simply mixing the liquid mixture and the inorganic solid powder. 6. The method of claim 5,
The waterproofing agent is an organic-inorganic composite binder composition that is an eco-friendly elastic coating waterproofing agent. A flame-retardant foamed styrofoam panel prepared by using the organic-inorganic composite binder composition according to claim 1 as a binder for foamed styrofoam. A non-flammable foamed glass bead panel, sound-absorbing body or buoy, characterized in that it is prepared by using the organic-inorganic composite binder composition according to claim 1 as a binder for foamed glass beads.

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