KR102171005B1 - Non-solvent two-component type paint composition for anti-static epoxy floor materials, method for preparing the same, and anti-static epoxy floor materials - Google Patents

Abstract

According to the present invention, an epoxy resin comprising 5 to 15% by weight of an epoxy resin reactive diluent, 40 to 60% by weight of calcium carbonate having an average particle size of 5 to 25 μm as an extender pigment, and 0.001 to 0.1% by weight of carbon nanotubes as a conductive material Part (A), and an epoxy curing agent part (B) comprising 30 to 80% by weight of an epoxy curing agent (amine resin), 10 to 40% by weight of a non-reactive diluent, and 5 to 30% by weight of a curing accelerator. A solvent-free two-part coating composition, a method for preparing the same, and an antistatic epoxy flooring material prepared therefrom are provided.
The solvent-free two-part coating composition according to the present invention is eco-friendly because it contains almost no volatile substances, and it is easy to work indoors, so it has high workability, and because a small amount or a small amount of carbon nanotubes are used as a conductive material, the physical properties of the matrix resin are reduced. Alternatively, an epoxy flooring material having excellent antistatic properties, abrasion resistance, and durability can be manufactured without damaging them.

Description

Non-solvent two-part coating composition for antistatic epoxy flooring, its manufacturing method, and antistatic epoxy flooring {NON-SOLVENT TWO-COMPONENT TYPE PAINT COMPOSITION FOR ANTI-STATIC EPOXY FLOOR MATERIALS, METHOD FOR PREPARING THE SAME, AND ANTI-STATIC EPOXY FLOOR MATERIALS}

The present invention relates to a solvent-free two-part coating composition for an antistatic epoxy flooring using carbon nanotubes (CNT) as a conductive material, a method for producing the same, and to an antistatic epoxy flooring, specifically, an epoxy resin, a diluent, A solvent-free two-part coating composition for an antistatic epoxy flooring comprising an epoxy resin portion (A) containing an extender pigment and a conductive material and an epoxy curing agent portion (B) containing an epoxy curing agent, a diluent and a curing accelerator, calcium carbonate as an extender pigment, It relates to a method for preparing the coating composition, characterized by the step of preparing a homogeneous mixture prepared from a trace amount of carbon nanotubes (CNT) and a reactive diluent as a conductive material, and to an antistatic epoxy flooring agent prepared from the coating composition.

An antistatic flooring material with excellent performance as a means to solve the problems in production due to the generation of static electricity such as semiconductor factories, hospital operating rooms, electronic product assembly factories, computer rooms, communication related facilities, etc. Is increasing in demand.

In other words, electrostatic discharge (ESD) is a level that usually causes discomfort to the human body, but may cause fatal damage such as malfunction or damage to internal circuits to electronic equipment. In the semiconductor field, micro-contamination of suspended particles occurs due to static electricity, and thus semiconductor chip defects may be caused.

Due to such problems, floor materials having antistatic or conductive properties are applied in clean rooms, electronic equipment assembly, laboratories, computers, electronic equipment installation areas, and medical facilities. In addition, the use of such conductive flooring is increasing even in places where there is a risk of flammability or explosion.

As a general flooring coating composition, an epoxy resin composition containing an epoxy resin and a curing agent is used, and a white conductive filler or a black conductive filler is used to impart antistatic performance to the coating film or to obtain the required suitable surface resistance. It adopts a method containing. If only white conductive filler is included, the epoxy resin composition is thickened due to the addition of a large amount of conductive filler, making roller work impossible during painting, or in some cases, it is difficult to meet the physical property standard of the surface resistance value.

Therefore, for the purpose of preventing the floor material from being charged, carbon black having excellent charging performance or a type of raw material doped with TiO ₂ has been used. In the case of carbon black, various colors are limited in implementation, and the TiO2 tin-doped type also has various problems such as limited dark color system, poor abrasion resistance, and light stains due to the thickness of the coating film. Is causing.

Patent Document 1 discloses a solvent-free epoxy flooring coating composition exhibiting a surface resistance of 5×10 ^{6 to 8} Ω, but as a conductive material, conductive zinc oxide 10 to 14 wt%, spherical white conductive pigment 10 to 14 wt% and Since it contains 25 to 30% by weight of a needle-shaped white conductive pigment, there is a problem that the physical properties of the film composition are deteriorated.

Patent Document 2 discloses a solvent-free epoxy flooring coating composition exhibiting a surface resistance of 5×10 ^{6 to 8} Ω, but a spherical white conductive pigment and a needle-shaped white conductive pigment limiting the conductivity absorption, particle size, and specific resistance to a specific range Since it contains a large amount, there is still a problem that the physical properties of the film composition are deteriorated.

Patent Document 3 discloses a technology capable of showing antistatic properties even when a floor material is formed thick by using an ionic liquid containing cations and anions selected from quaternary nitrogen or phosphorus compounds as a conductive material. However, in order to exhibit satisfactory antistatic properties, fillers and/or pigments having conductive properties, such as carbon fiber, graphite, carbon black, metal (alloy) oxide, and/or fillers and/or pigments coated therewith may be additionally added. There is a problem that it needs to be used.

Patent Document 4 relates to an epoxy-based electrostatic dispersing and antistatic conductive flooring material having static absorption and dispersing properties, and proposes the use of a conductive composite filler such as carbon black, rechargeable material, earth graphite, etc., which contain carbon and have electrical conductivity. .

In order to manufacture antistatic coatings, films, and flooring, carbon-based materials such as carbon black and graphite, conductive materials such as metal materials, and conductive polymers, or antistatic agents are mixed with the matrix resin, but in order to obtain satisfactory surface resistance There is a problem that it is necessary to add these to the matrix resin in large amounts, and this may deteriorate other physical properties or performance of the matrix resin.

Accordingly, materials that can exhibit satisfactory antistatic properties even with small or small additions have been proposed, and among them, the possibility of carbon-based nanomaterials such as carbon nanotubes and graphene has emerged.

However, it has been reported that carbon nanotubes can exhibit excellent antistatic properties even when a very small amount is used as a conductive material, but their use has been limited due to low dispersibility in organic materials.

In general, since carbon nanotubes as a conductive material have low dispersibility with organic substances such as organic solvents, in order to obtain a coating composition having satisfactory antistatic properties, a large amount of carbon nanotubes or carbon nanotubes Is modified, or a special dispersion method or dispersion aid is used. However, the method of using a large amount of carbon nanotubes is economically very disadvantageous because carbon nanotubes are very expensive compared to other conductive materials such as carbon black, graphite, and metal. A method of improving dispersibility with an organic material by modifying or modifying carbon nanotubes, and a method of using another dispersion method or a dispersant, etc., are economically disadvantageous because additional cost is consumed.

Accordingly, many studies are being conducted to develop a method for effectively and economically manufacturing an epoxy flooring material, film, etc. using a small amount or a very small amount of carbon nanotubes as a conductive material.

Korean Patent Publication No. 10-2000-0047277 (published on July 25, 2000) Republic of Korea Patent Application Publication No. 10-2001-0058990 (published on Jun. 2001) International Publication No. WO2007/115750 (published on October 18, 2007) Republic of Korea Patent Publication 10-1210228 (2012.12.04 registered)

The present inventors have studied for many years to develop a method for effectively and economically manufacturing an epoxy flooring material using a small amount or a very small amount of carbon nanotubes as a conductive material.

The present inventors are a solvent-free two-part type for an antistatic epoxy flooring comprising an epoxy resin portion (A) containing an epoxy resin, a diluent, an extender pigment and a conductive material, and an epoxy curing agent portion (B) containing an epoxy curing agent, a diluent and a curing accelerator. In the coating composition, when the epoxy resin portion (A) is prepared by adding a reactive diluent as a diluent as a diluent, an extender pigment, and a carbon nanotube as a conductive material to the epoxy resin, a small amount or a trace amount of the carbon nanotubes as a conductive material, even epoxy The present invention was completed by discovering that it can exhibit excellent antistatic properties even when it contains less than 0.1% by weight of the resin portion (A).

The solvent-free two-component coating composition for an antistatic epoxy flooring material according to the present invention is eco-friendly because it contains almost no volatile substances, has high workability due to easy indoor work, and uses a small amount or a small amount of carbon nanotubes as a conductive material, An epoxy flooring material having excellent antistatic properties, abrasion resistance, and durability can be manufactured without deteriorating or damaging the physical properties of the matrix resin.

The first object of the present invention is composed of an epoxy resin portion (A) containing an epoxy resin, a reactive diluent, an extender pigment and conductive particles, and an epoxy curing agent portion (B) containing an epoxy curing agent, a non-reactive diluent and a curing accelerator. To provide a solvent-free two-part coating composition for antistatic epoxy flooring,

The extender pigment has an average particle size of 5 to 25 μm, and may be selected from the group consisting of calcium carbonate, barium sulfate, aluminum silicate, talc, silica powder, diatomaceous earth, silica, alumina and titania,

The conductive material may be selected from the group consisting of carbon nanotubes, fullerenes, graphene and tanno nanofibers,

According to one preferred embodiment of the present invention, the extender pigment and the conductive material may be used in the form of a wet grinding mixture by wet grinding in a liquid organic medium such as a non-reactive diluent or a reactive diluent.

According to one embodiment of the present invention, the extender pigment and the conductive material may be used in an amount of 30 to 70% by weight and 0.001 to 0.1% by weight, respectively, based on the total weight of the epoxy resin part (A). .

According to one embodiment of the present invention,

The epoxy resin portion (A) is 10 to 50% by weight of an epoxy resin, preferably 20 to 40% by weight, 30 to 70% by weight of an extender pigment, preferably 40 to 60% by weight, and 1 to 5% by weight of a pigment component, Preferably 1 to 4% by weight, conductive material 0.001 to 0.2% by weight, preferably 0.001 to 0.1% by weight, and for example 5 to 15% by weight, preferably 7 to 12% by weight of a reactive diluent containing an epoxy group Contains,

The epoxy curing agent portion (B) is an epoxy curing agent (amine resin) 30 to 80% by weight, preferably 40 to 70% by weight, non-reactive diluent 10 to 40% by weight, preferably 15 to 35% by weight, and a curing accelerator It may contain 5 to 30% by weight, preferably 5 to 25% by weight.

A second object of the present invention is to provide a method for preparing a solvent-free two-part coating composition for an antistatic epoxy flooring comprising the following steps:

(1a) adding an extender pigment and a conductive material to the reactive diluent, and wet grinding to prepare a wet grinding mixture,

(1b) to the obtained wet grinding mixture, an epoxy resin, an additional extender pigment, a pigment component and an additional reactive diluent were added and mixed to prepare an epoxy resin portion (A), and

(2) An epoxy curing agent part (B) is prepared by mixing an epoxy curing agent, a diluent, and a curing accelerator.

The present invention will be described in more detail below.

In general, epoxy resins can be widely used in a variety of applications in combination with a suitable curing agent. The excellent adhesion property of the epoxy flooring coating composition to the concrete base is recognized as a major advantage, and it is suitable for use in high-functional paints because of its low shrinkage and high mechanical and chemical resistance compared to other types of paints to protect concrete. .

Currently commercialized epoxy flooring systems can be largely classified into two types, solvent-free and solvent-free. For the solvent type, a thin film type (dry film thickness of about 300 μm) and a solvent-free type (dry coating thickness of about 300 μm) with roller coating twice in the middle and top coat are coated with a thick film (dry coating thickness of about 2000 μm or more). There is a thick film type that coats the roller once. In the case of the solvent type, since a large amount of volatile solvent is used to obtain a coating film having good roller workability and leveling, there is a problem that it is harmful to the air environment and to the health of the worker. In addition, in order to obtain a coating film of at least 200 μm or more in order to function as a flooring material, the solvent type requires at least two coatings due to the characteristics of the solvent type paint with a low solids volume ratio. This generally requires drying for about 1 day at room temperature for repainting after coating once, which leads to an increase in work period and man-hours of at least 2 days.

On the other hand, as the solvent-free type, there is a thick film type (self-leveling type) in which 2000 µm or more is coated using a reki or the like. In the case of existing solvent-free paints, it is for self-leveling, not for roller painting, and a good appearance can be formed only when the thickness of the coating film is more than 2000㎛. Accordingly, the amount of paint required increases and construction cost is greatly increased and chemical resistance, etc. There is an inconvenience of having to paint a solvent-type top coat to complement the physical properties of the product.

These epoxy flooring materials are most widely used and are used as flooring materials in many fields, but development of antistatic epoxy flooring materials has been insufficient. Therefore, a technology for economically and effectively imparting antistatic properties to an epoxy flooring material is still an important technical task, and many studies have been conducted until recently.

The present invention is a solvent-free two-part paint for antistatic epoxy flooring comprising an epoxy resin portion (A) containing an epoxy resin, a diluent, an extender pigment and a conductive material, and an epoxy curing agent portion (B) containing an epoxy curing agent, a diluent and a curing accelerator. The composition, a method for preparing the same, and the resulting antistatic epoxy flooring material will be described in detail below in sequence.

(A) Epoxy resin part

In the solvent-free two-part coating composition for an antistatic epoxy flooring material of the present invention, the epoxy resin portion (A) contains 10 to 50% by weight of an epoxy resin, 30 to 70% by weight of an extender pigment, 1 to 5% by weight of a pigment component, and conductivity. 0.001 to 0.2% by weight of the substance, and 5 to 15% by weight of a diluent.

The epoxy resins include bisphenol A type epoxy (DGEBA Type Epoxy), bisphenol F type epoxy (DGFBF Type Epoxy), novolac type epoxy, brominated epoxy, cycloaliphatic epoxy, and rubber modified. Epoxy (Rubber Modified Epoxy), aliphatic glycidyl type epoxy (Aliphatic Polyglycidyl Type Epoxy), glycidyl amine type epoxy (Glycidyl Amine Type Epoxy), etc., BPA (bisphenol A) and epichlorohydrine (Epichlorohydrine, ECH) Bisphenol A type epoxy prepared by reacting (DGEBA Type Epoxy) may be mentioned in particular.

The extender pigments are not particularly limited, and those commonly used as extender pigments in the epoxy flooring material may be used, and generally 30 to 70% by weight, specifically 40 to 60% by weight, based on the total weight of the epoxy resin part (A), Preferably it can be used in an amount of 45 to 55% by weight.

As the extender pigment, inorganic particles or metal oxide particles may be used, for example, barium sulfate (precipitate barium sulfate, Baryte, etc.), aluminum silicate (clay, kaolin, bentonite, etc.), and bone stone powder (talk) as inorganic particles. ), silica powder, diatomaceous earth, etc. may be mentioned, and silica, titania, alumina, zirconia, and the like may be mentioned as metal oxide particles, but are not limited thereto.

According to one embodiment of the present invention, the extender pigment has an average particle size of generally 1 to 500 µm, specifically 5 to 25 µm, and preferably 10 to 20 µm. According to a preferred embodiment of the present invention, the extender pigment has an average particle size of generally 1 to 500 µm, specifically 5 to 25 µm, preferably 10 to, in the resulting epoxy resin part (A) or during its manufacturing process. It may be pulverized to be 20 μm or selected from those that may have the particle size.

If the particle size of the extender pigment in the wet grinding mixture is out of the above range (1 to 500 μm, specifically 5 to 25 μm, preferably 10 to 20 μm), the extender pigment particles pulverize the aggregate of the conductive material in the wet grinding process. And the effect of maintaining the dispersion of the pulverized nanoparticles is reduced, and thus the aggregates are added or the dispersion is insufficient.

According to one embodiment of the present invention, when calcium carbonate is used as the extender pigment, it is possible to provide a flooring material having low noise characteristics in addition to antistatic properties. For example, the calcium carbonate is 35 to 45% by weight of hard calcium carbonate with a particle size of 0.8 to 3 µm that can be used as a reinforcing filler, and 5 to ultra-fine calcium carbonate with a particle size of 0.03 to 0.08 µm that can be used as a functional active filler. It may be included in an amount of 15% by weight.

In general, in the manufacture of a paint composition, the lower the ratio of solid fillers such as extender pigments, the lower the thixotropy of the paint composition, making it impossible to obtain an uneven finish by roller painting, and the higher the ratio, the more workability during roller painting. It is known that it is poor and it is difficult to form irregular patterns of a certain size. Therefore, in selecting calcium carbonate as an extender pigment, it may be desirable to select and use a particle size in an appropriate ratio as in the ratio of the use of the reinforcing filler and the functional filler.

When inorganic particles such as calcium carbonate are selected as the extender pigment and applied as a functional filler, dispersibility by coating the surface of the extender pigment particles with fatty acids such as stearic acid, oleic acid, and glycerin. It is also possible to impart thixotropy to the paint by increasing it. In this case, in the method of surface treatment of inorganic particles such as calcium carbonate with fatty acids, fine particles of calcium carbonate and fatty acids are mixed at a predetermined ratio and dispersed at a high speed so that each calcium carbonate particle is coated with fatty acids.

In the epoxy resin portion (A) of the two-part coating composition of the present invention, the pigment component is a component that gives a coloring effect, and may be selected and mixed from lead chromate salt, iron oxide, etc., but is not limited thereto.

In general, diluents are used to reduce viscosity and adjust solution flow, and unlike solvents, they do not volatilize and refer to components that remain in the cured product upon curing. For example, benzyl alcohol, dibutylphthalate ; Non-reactive diluents such as DBP) and phenolic resin (nonyl-phenol) are used. On the other hand, in order to dilute high viscosity epoxy resins based on bisphenol-A, bisphenol-F and novolac and other polymers such as polyurethanes and acrylics, a reactive diluent selected from epoxy group-containing compounds is used.

The reactive diluent for use in the present invention is a low viscosity epoxy group-containing compound having an aliphatic or aromatic structure, for example a glycidyl ether or glycidyl ester having 1 to 3 epoxy groups. Typical examples of the reactive diluent include mono-, di- or triglycidyl ethers of C ₆ to C ₁₄ monoalcohol or alkylphenol ; Monoglycidyl ether of cashew nut shell oil; Ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 1,4-butylene glycol, 1,5-pentanediol, 1,6-hexane Diglycidyl ether of diol and cyclohexanedimethanol ; Triglycidyl ether of trimethylolpropane ; And glycidyl esters of C6 to C24 carboxylic acids or mixtures thereof.

Alternatively, as a specific example of a glycidyl ether or glycidyl ester having an aliphatic or aromatic structure and having 1 to 3 epoxy groups, n-butyl glycidyl ether, aliphatic glycidyl ether, 2-ethylhexyl gly Cidyl ether, phenyl glycidyl ether, O-cresyl glycidyl ether, nonylphenyl glycidyl ether, p-tertbutylphenyl glycidyl ether, 1.4-butanediol diglycidyl ether, 1.6-hexanedioldi Glycidyl ether, neopentyl glycidyl ether, 1.4-cyclohexanedimethylol diglycidyl ether, polypropylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, diethylene Glycol diglycidyl ether, resorcinol diglycidyl ether, hydrogenate bisphenol iglycidyl ether, trimethylolpropene triglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether , Penteritritol Polyglycidyl Ether, Kestolglycidyl Ether, Serbitol Polyglycidyl Ether, Neokenoxed Glycidyl Ether, diglycidyl-1.2-cyclonucleic acid dicarboxylate, diglyci Dyl-O-phthalate, n,n-diglycidylamine, n,n-diglycidyl-O-toludiene, triglycidyl-p-aminophenol, tetraglycidyl-diaminodiphenylmethane, Triglycidyl-isocyanate, 1.4-butanediol diglycidyl ether, 1.6-hexanediol diglycidyl ether, polypropylene glycidyl diglycidyl ether, triethylolpropene triglycidyl ether selected from the group consisting of It is possible to use one or more reactive diluents, but is not limited thereto.

In the present invention, an epoxy group-containing compound, for example, a low viscosity glycidyl ether or a derivative thereof may be used as the reactive diluent, and commercially available products include Catana™ EPOX (manufactured by SACHEM, Inc.), 1.6HDGE, DGDE, GOT, GAN (manufactured by Cheil Chemicals), Cardura™ E10 (Hexion), and the like can be illustrated.

As the carbon nanotubes (CNT, Carbon Nanotube) usable in the present invention, single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanotube bundles, etc. may be mentioned, but are not limited thereto, Other carbon allotropes such as fullerene, graphene, nanowires, and nanorods may be included. The carbon nanotube used as the conductive material in the present invention is generally 0.001 to 0.2% by weight, specifically 0.002 to 0.1% by weight, preferably 0.005 to 0.05% by weight based on the total weight of the epoxy resin portion (A). It is used as a content.

(B) Epoxy curing agent part

In the non-solvent two-part coating composition for an antistatic epoxy flooring material of the present invention, the epoxy curing agent part (B) may contain 10 to 40 wt% of an epoxy curing agent (amine resin) non-reactive diluent and 5 to 30 wt% of a curing accelerator. have.

The epoxy curing agent may be polyamide classified as a modified aliphatic amine among amine-based curing agents in terms of chemical structure. As the diluent, benzyl alcohol, dibutylphthalate (dibutylphthalate; DBP), which are non-reactive diluents described above, may be used. ), phenolic resin (nonyl-phenol), especially phenolic resin (dodecylphenol), can be used to control the final viscosity of the paint.

The epoxy curing agent part (B) may further contain an additive such as a solvent, a thickener, a dispersant, a dispersing aid, and the like in an amount of 0.1 to 5% by weight, and the additive may be preferably selected from a carbon-based compound.

In general, a solvent-free two-part coating composition for epoxy flooring consisting of (A) an epoxy resin portion and (B) an epoxy curing agent portion is sufficiently dispersed and stirred in each stirring tank for 20 to 30 minutes or longer, and then cooled to room temperature, and then ( The composition is packaged by reacting and curing component A) and component (B), and then coating the surface to be coated with a coating thickness of 1,000 to 3,000 microns using a requis or the like. At this time, for the curing reaction, (A) epoxy resin part and (B) epoxy curing agent part are mixed at a weight ratio of 5:1, stirred at 1500 rpm for 5 minutes, and components (A) and (B) are mixed within pot life. The packaging by roller coating can be completed within the maximum available time).

(C) Method for producing a two-part coating composition

The solvent-free two-part coating composition for an antistatic epoxy flooring according to the present invention can be prepared by a method comprising the following steps:

(1a) wet grinding of an extender pigment and a conductive material in a liquid organic medium to prepare a wet grinding mixture,

(1b) mixing the wet grinding mixture, an epoxy resin, an additional extender pigment, a pigment component and an additional reactive diluent to prepare an epoxy resin portion (A), and

(2) An epoxy curing agent part (B) is prepared by mixing an epoxy curing agent, a diluent, and a curing accelerator.

In the above step (1a), the organic medium may be selected from the above-mentioned reactive diluents or non-reactive diluents, preferably from reactive diluents. In some cases, an organic solvent or an organic solvent commonly used in the paint field, for example, ether, ester, alcohol, benzene, toluene, kerosene, etc. may be used as the organic medium.

In the step (1a), the amount of the extender pigment, the conductive material, and the organic medium is not strictly limited, but, for example, 30 to 70% by weight of the extender pigment, 0.01 to 2% by weight of the conductive material, 25 It may be selected from -50% by weight and 5-20% by weight of other components. The other components may be selected from non-reactive diluents, organic solvents, dispersants, dispersants, thickeners, and the like.

In the step (1b), the amount of the wet grinding mixture, the epoxy resin, the calcium carbonate as an extender pigment, the pigment component and the reactive diluent are not particularly limited, and in the resulting epoxy resin portion (A), the epoxy resin 10 to 50% by weight, preferably 20 to 40% by weight, 30 to 70% by weight of calcium carbonate, preferably 40 to 60% by weight, pigment component 1 to 5% by weight, preferably 1 to 4% by weight, carbon nanotubes It may be used in an amount of 0.001 to 0.2% by weight, preferably 0.001 to 0.1% by weight, and 5 to 15% by weight of the reactive diluent, preferably 7 to 12% by weight.

In the above step (2), the epoxy curing agent (amine resin), the non-reactive diluent and the curing accelerator are, in the resulting epoxy curing agent part (B), 30 to 80% by weight of the epoxy curing agent (amine resin), preferably 40 to 70 It may be used in an amount of 10 to 40% by weight, preferably 15 to 35% by weight, and 5 to 30% by weight of a curing accelerator, preferably 5 to 25% by weight of a non-reactive diluent. In some cases, an optional additive may be further used in an amount of 0.1 to 10% by weight.

According to one embodiment of the present invention, the wet grinding mixture of an extender pigment and a conductive material in the above-described step (1a) is applied to an organic medium selected from a reactive diluent, an extender pigment such as calcium carbonate, and a conductive material such as carbon nanotubes. The substance can be added and obtained in the form of a homogeneous mixture by wet grinding using a ball mill or the like. The above-described extender pigment may have an average particle size of approximately 5 to 25 μm, or may be selected from materials that may have the average particle size after wet grinding.

According to one embodiment of the present invention, calcium carbonate and carbon nanotubes are added to the reactive diluent, and the average particle size of the calcium carbonate is approximately 5 to 25 µm or wet pulverization or under the condition of maintaining the average particle size. By grinding, a wet-milled mixture of calcium carbonate and carbon nanotubes can be obtained in the form of a homogeneous mixture.

According to one variant of the present invention, mixing and dispersing of an extender pigment and a conductive material may be promoted or assisted by a method such as ultrasonic grinding.

In general, since carbon-based conductive materials such as carbon nanotubes have low dispersibility with organic materials such as organic solvents, in order to obtain a coating composition having satisfactory antistatic properties, they are used in large amounts, or surface modified or modified. Or, it is carried out using a special dispersion method or dispersion aid. However, conductive materials such as carbon nanotubes, fullerenes, and graphene are economically disadvantageous because they are very expensive compared to other conductive materials such as carbon black, graphite, and metal, and they are separated from organic materials by surface modification or surface modification. The method of increasing the acidity or the use of other special dispersion methods or dispersants is economically disadvantageous because additional costs are consumed.

In the present invention, if expensive conductive materials such as carbon nanotubes, fullerenes, graphene, etc. are used in the form of a wet grinding mixture with an extender pigment such as calcium carbonate, excellent antistatic properties even if the conductive material is contained in a very small amount. There is an advantage of being able to represent.

One of the advantages of the present invention is to use carbon-based nanoparticles such as carbon nanotubes, fullerenes, and graphene as a conductive material, so that it is widely used in the prior art (eg, carbon black, graphite, conductive metal, etc.). Compared to the fact that it is used in a very small amount or in a very small amount, it shows excellent antistatic properties and abrasion resistance.

Another advantage of the present invention is that the amount of conductive material used is very small, so it solves the problem of gloss stains according to the roller pattern, abrasion resistance defects caused by high PVC%, and increases durability, which is an advantage of epoxy lining, It is that it can increase satisfaction.

Another advantage of the present invention is that it is possible to easily and economically form an epoxy flooring material having a dry coating thickness of 1 to 3 mm and exhibiting high antistatic properties and/or noise prevention properties.

Another advantage of the present invention is that when calcium carbonate is used as an extender pigment, an antistatic flooring material having excellent low noise characteristics and smoothness can be prepared.

Another advantage of the present invention is that since the coating composition is manufactured in a solvent-free two-part type, it has excellent long-term storage, and it is easy to paint using a rake or a spatula as well as roller or spray coating, so that the workability is excellent. to be.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these examples.

Example 1

(1a) Preparation of carbon nanotube paste:

In a cylindrical reactor, 35 parts by weight of a reactive diluent (Cardura E10P) and 0.5 parts by weight of a dispersant (Tego Disperse 673) were added and stirred at 800 rpm for 10 minutes. Here, 28.5 parts by weight of calcium carbonate (CaCO ₃ ) as an extender pigment and 1 part by weight of CNT (10%) as a conductive material are sequentially slowly added under stirring, and then further stirred at 1000 rpm for 5 minutes and 1500 rpm for 30 minutes. . The resulting mixture was ground with a sand mill at 3,000 rpm until the dispersed particle size of calcium carbonate became 20 μm, and the viscosity was adjusted by additionally adding 35 parts by weight of a reactive diluent to prepare a carbon nanotube paste.

(1b) Preparation of epoxy resin portion (A):

In a cylindrical reactor, 30 parts by weight of an epoxy resin (DER331, Dow Chemicals), 3 parts by weight of butyl glycidyl ether as a reactive diluent, 0.4 parts by weight of Disperbyk-110 (Solution of a copolymer with acidic groups) as a wetting and dispersing agent, BYK as a defoaming agent 0.4 parts by weight of -066N (polysiloxane solution, manufactured by BYK) was added and stirred at 1,000 rpm for 10 minutes. Here, 0.2 parts by weight of fumed silica, 50 parts by weight of calcium carbonate as an extender, 0.4 parts by weight of the carbon nanotube paste obtained in step (1a), and 15.6 parts by weight of a non-reactive diluent were further added, and 1,200 rpm. By dispersing over time, an epoxy resin portion (A) was prepared.

(2) Preparation of epoxy curing agent part (B):

In a cylindrical reactor, 50 parts by weight of an amine resin (Jeffamine D230), 40 parts by weight of a non-reactive diluent (dodecylphenol, hydrocarbon-based) and 10 parts by weight of a curing accelerator (DMP-30) were all added and stirred for 1 hour to make epoxy To prepare the curing agent part (B).

Example 2

In step (1a) of Example 1, the amount of reactive diluent was changed from 35 parts by weight to 30 parts by weight, the amount of calcium carbonate used was changed from 28.5 parts by weight to 38.5 parts by weight, and the amount of the reactive diluent added was changed from 35 parts by weight to 30 parts by weight. Except for preparing the carbon nanotube paste, the procedure was the same as in Example 1.

Comparative Example 1

In step (1a) of Example 1, the amount of the reactive diluent was changed from 35 parts by weight to 30 parts by weight, the amount of calcium carbonate used was changed from 28.5 parts by weight to 38.5 parts by weight, and the amount of the added reactive diluent was changed from 35 parts by weight to 30 parts by weight. And, except that the particle size of calcium carbonate was adjusted from 20 μm to 1 μm to prepare a carbon nanotube paste, the same procedure as in Example 1 was performed.

Comparative Example 2

In step (1a) of Example 1, an epoxy resin was used in an amount of 50 parts by weight instead of the reactive diluent, calcium carbonate was not used, and the amount of the reactive diluent was changed from 35 parts by weight to 48.5 parts by weight to prepare a carbon nanotube paste. Except that, it proceeded in the same manner as in Example 1.

Reference Example 1

The procedure was the same as in Comparative Example 1, except that a carbon nanotube paste was prepared by increasing the carbon nanotubes from 1 part by weight to 10 parts by weight without using potassium carbonate.

In Table 1 below, the ingredients used in the Examples, Comparative Examples and Reference Examples and their contents are described. In Table 2 below, a flooring material was prepared using the two-component epoxy coating composition obtained in the Examples, Comparative Examples and Reference Examples, and the appearance and antistatic properties of the resulting flooring material were measured and described.

step ingredient Example 1 Example 2 Comparative Example 1 Comparative Example 2 Reference Example 1 1a Epoxy resin - - - 50 - Reactive diluent 35 30 30 - 35 Dispersant 0.5 0.5 0.5 0.5 0.5 CaCO ₃ (1㎛) - - 38.5 - - CaCO ₃ (20㎛) 28.5 38.5 - - - CNT (10%) One One One One 10 Reactive diluent 35 30 30 48.5 54.5 Sum 100 100 100 100 100 1b Epoxy resin 30 30 30 30 30 Reactive diluent 3 3 3 3 3 Disperbyk-110 0.4 0.4 0.4 0.4 0.4 BYK-066N 0.4 0.4 0.4 0.4 0.4 Fumed Silica 0.2 0.2 0.2 0.2 0.2 Extender Pigment (Calcium Carbonate) 50 50 50 50 50 Prepared in step 1a
CNT paste 0.4 0.4 0.4 0.4 0.4 Non-reactive diluent 15.6 15.6 15.6 15.6 15.6 Sum 100 100 100 100 100

Properties and appearance Example 1 Example 2 Comparative Example 1 Comparative Example 2 Reference Example 3 Antistatic 10 ⁶ ∼ 10 ⁹ 10 ⁶ ∼ 10 ⁸ 10 ⁷ ∼ 10 ¹⁰ 10 ¹⁰ ∼ 10 ¹¹ 10 ⁹ ∼ 10 ¹⁰ Film smoothness Good usually Bad Bad Bad

As can be seen in Tables 1 and 2, when a CNT paste containing calcium carbonate and carbon nanotubes with a particle size adjusted first is prepared and then mixed with an epoxy resin to prepare an epoxy resin portion (A) (Example 1 And 2), the resulting flooring material has excellent antistatic properties and has good or normal coating film smoothness, so it can be seen that it can be preferably used as an antistatic flooring material.

On the other hand, when a CNT paste was prepared using calcium carbonate with too small particle size and then mixed with an epoxy resin to prepare the epoxy resin part (A) (Comparative Example 1), not only the antistatic property was slightly lowered, but also the coating film smoothness It was bad. When the carbon nanotubes were dispersed without using calcium carbonate (Comparative Example 2), both antistatic properties and coating film smoothness were poor.

For reference, if calcium carbonate was not used, but a CNT paste containing an excess of carbon nanotubes was first prepared and then mixed with an epoxy resin to prepare the epoxy resin part (A) (Reference Example 1), a trace amount of carbon nanotubes The antistatic property was poorer than when a tube was used. As a result of this, an excellent dispersion effect of carbon nanotubes can be achieved by using calcium carbonate in the present invention, whereby the flooring material of the present invention can have an excellent antistatic effect even if it contains a trace amount of carbon nanotubes. Proves indirectly.

The present invention can be used in the paint industry, building industry, automobile industry, and the like.

Claims (8)

A solvent-free agent for antistatic epoxy flooring consisting of an epoxy resin part (A) including an epoxy resin, a reactive diluent, an extender pigment and a conductive material, and an epoxy curing agent part (B) including an epoxy curing agent, a non-reactive diluent and a curing accelerator. As a liquid coating composition,
The extender pigment has an average particle size of 5 to 25 μm, and may be selected from the group consisting of calcium carbonate, barium sulfate, aluminum silicate, talc, silica powder, diatomaceous earth, silica, alumina and titania,
The conductive material is a carbon nanotube,
The extender pigment and carbon nanotubes are used in the form of a wet grinding mixture obtained by wet grinding in a liquid organic medium,
The epoxy resin part (A) contains 20 to 40% by weight of an epoxy resin, 30 to 70% by weight of an extender pigment, 1 to 5% by weight of a pigment component, 0.001 to 0.2% by weight of carbon nanotubes, and 5 to 15% by weight of a reactive diluent. So,
Surface resistance is 10 ⁶ to 10 ⁹ Ω / sq, characterized in that, antistatic epoxy flooring, solvent-free two-component coating composition.
delete The method of claim 1,
Antistatic, characterized in that the epoxy curing agent part (B) contains 30 to 80% by weight of an epoxy curing agent (amine resin), 10 to 40% by weight of a non-reactive diluent, 5 to 30% by weight of a curing accelerator, and other carbon compounds. Solvent-free two-part coating composition for epoxy flooring.
The method of claim 1,
The reactive diluent is a glycidyl ether or glycidyl ester having an aliphatic or aromatic structure and having 1 to 3 epoxy groups, a solvent-free two-part coating composition for an antistatic epoxy flooring.
As a method for producing a solvent-free two-part coating composition for an antistatic epoxy flooring according to claim 1,
(1a) preparing a wet grinding mixture by wet grinding the extender pigment and the conductive material in a liquid organic medium;
(1b) preparing an epoxy resin portion (A) by mixing the wet grinding mixture, an epoxy resin, an additional extender pigment, a pigment component, and a reactive diluent; And
(2) preparing an epoxy curing agent part (B) by mixing an epoxy curing agent, a non-reactive diluent, and a curing accelerator; including,
The extender pigment has an average particle size of 5 to 25 μm, and may be selected from the group consisting of calcium carbonate, barium sulfate, aluminum silicate, talc, silica powder, diatomaceous earth, silica, alumina and titania,
The conductive material is a carbon nanotube,
The epoxy resin portion (A) prepared in step (1b) is 20 to 40% by weight of epoxy resin, 30 to 70% by weight of extender pigment, 1 to 5% by weight of pigment component, 0.001 to 0.2% by weight of carbon nanotubes, and reactive diluent. It contains 5 to 15% by weight,
The solvent-free two-part coating composition for an antistatic epoxy flooring prepared by the above manufacturing method is characterized in that the surface resistance is 10 ⁶ to 10 ⁹ Ω/sq,
Method for producing a solvent-free two-component coating composition for antistatic epoxy flooring.
The method of claim 5,
In the step (1a), 30 to 69.9% by weight of an extender pigment, 0.1 to 2% by weight of a conductive material, 25 to 50% by weight of a reactive diluent, and 5 to 20% by weight of an additive are used. Method for producing a solvent-free two-component coating composition for epoxy flooring.
delete An antistatic epoxy flooring prepared from the solvent-free two-part coating composition according to any one of claims 1, 3 to 4.