KR20190140623A - 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

The present invention provides: a solvent-free two liquid type paint composition for an antistatic epoxy flooring material which comprises an epoxy resin part (A) including 5 to 15 wt% of epoxy resin reactive diluent, 40 to 60 wt% of calcium carbonate having an average particle size of 5 to 25 μm as an extender pigment, and 0.001 to 0.1 wt% of carbon nanotubes as a conductive material and an epoxy curing agent part (B) including 30 to 80 wt% of epoxy curing agent (amine resin), 10 to 40 wt% of non-reactive diluent, and 5 to 30 wt% of a curing accelerator; a producing method thereof; and an antistatic epoxy flooring material produced thereby. The solvent-free two liquid type paint composition according to the present invention: is environmentally friendly with almost no volatile material; has high workability by being easy to work indoors; and is able to produce an epoxy flooring material with excellent antistatic properties, abrasion resistance, and durability without degrading or damaging the physical properties of matrix resin by using a small or very small amount of carbon nanotubes as a conductive material.

Description

Solvent-free two-part coating composition for antistatic epoxy flooring, preparation method thereof, and antistatic epoxy flooring TECHNICAL EPOXY FLOOR MATERIALS}

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

Antistatic flooring with excellent performance as a means to solve the problem that may cause disruption to production or harmful effects on human body such as semiconductor factory, hospital surgery room, electronic product assembly factory, computer room, communication related facilities, etc. Demand is increasing.

In other words, electrostatic discharge (ESD) is generally unpleasant to the human body, but may cause fatal damage to electronic equipment such as malfunction or damage to internal circuits. In the semiconductor field, fine contamination of suspended particles occurs due to static electricity, which may result in semiconductor chip defects.

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

As a general floor 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 required surface resistance. The method of containing is adopted. When only the white conductive filler is included, a large amount of conductive filler is added, thereby increasing the epoxy resin composition, making it impossible to perform roller work during painting, or in some cases, it is difficult to meet the physical property criteria of surface resistance.

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

Patent Literature 1 discloses a solvent-free epoxy floor coating composition having a surface resistance of 5 × 10 ^{6 to 8} Ω. However, as a conductive material, 10-14% by weight of conductive zinc oxide, 10-14% by weight of spherical white conductive pigment, and It contains 25-30 weight% of needle-shaped white electroconductive pigments, and there exists a problem that the physical property of a film composition falls.

Patent Literature 2 discloses a solvent-free epoxy flooring coating composition exhibiting a surface resistance of 5 × 10 ^{6 to 8} Ω. However, spherical white conductive pigments and needle-shaped white conductive pigments have limited conductive absorption, particle size, and specific resistance to a specific range. There is still a problem that a large amount is contained and the physical properties of the coating composition are lowered.

Patent document 3 discloses a technique capable of exhibiting antistatic properties even when the floor is thickly formed by using an ionic liquid containing a cation and an anion selected from quaternary nitrogen or phosphorus compounds as the conductive material. However, in order to exhibit satisfactory antistatic properties, additionally fillers and / or pigments having conductive properties such as carbon fibers, graphite, carbon black, metal (alloy) oxides and / or fillers and / or pigments coated with them There is a problem that needs to be used.

Patent document 4 relates to an epoxy-based electrostatic dispersion and an antistatic conductive flooring having electrostatic absorption dispersion characteristics, and proposes the use of a conductive composite filler such as carbon black, carbonaceous material, earth graphite, and the like containing carbon and having electrical conductivity. .

In order to produce an antistatic coating, a film, and a flooring material, a carbon-based material such as carbon black, graphite, a metal material, a conductive material such as a conductive polymer or an antistatic agent are mixed with the matrix resin, but in order to obtain satisfactory surface resistance There is a problem that it is necessary to add them in a large amount to the matrix resin, which may lower other physical properties or performance of the matrix resin.

Therefore, a material that can exhibit satisfactory antistatic properties even with a small amount or a small amount of addition has been proposed, and the possibility of carbon-based nanomaterials such as carbon nanotubes and graphene has been highlighted.

However, although carbon nanotubes have been reported to exhibit excellent antistatic properties even when using trace amounts as conductive materials, their use has been limited due to their low dispersibility in organic materials.

In general, carbon nanotubes as conductive materials have low dispersibility with organic materials such as organic solvents, so that carbon nanotubes containing a large amount of carbon nanotubes or carbon nanotubes may be used to obtain a coating composition having satisfactory antistatic properties. Or special dispersion methods or dispersing aids are used. However, the method of using a large amount of carbon nanotubes is very economically disadvantageous because carbon nanotubes are very expensive compared to other conductive materials such as carbon black, graphite, and metal. The method of modifying or modifying carbon nanotubes to increase dispersibility with organic materials and using other dispersing methods or dispersants is also economically disadvantageous because of the additional cost.

Therefore, many studies have been conducted to develop a method for effectively and economically manufacturing an epoxy flooring material, a film, or the like using a small amount or a very small amount of carbon nanotubes as a conductive material.

Republic of Korea Patent Publication No. 10-2000-0047277 (July 25, 2000) Republic of Korea Patent Publication No. 10-2001-0058990 (Jul. 2001. Publication) International Publication WO2007 / 115750 (Published October 18, 2007) Republic of Korea Patent Registration 10-1210228 (2012.12.04.Registration)

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

The inventors of the present invention provide a solvent-free two-component type antistatic epoxy flooring comprising an epoxy resin portion (A) containing an epoxy resin, a diluent, a sieving pigment and a conductive material, and an epoxy curing agent portion (B) including 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 carbon nanotube as a diluent, a reactive diluent, a sieving pigment, and a conductive material to the epoxy resin, a small amount or a small amount of carbon nanotube as a conductive material, even epoxy The present invention has been completed by discovering that excellent antistatic properties can be exhibited even when contained in 0.1% by weight or less of the resin portion (A).

Solvent-free two-component coating composition for antistatic epoxy flooring according to the present invention is environmentally friendly, almost no volatiles, easy to work indoors, high workability, because a small amount or a small amount of carbon nanotubes are used as the conductive material, Epoxy flooring having excellent antistatic property, abrasion resistance, and durability can be produced without degrading or damaging the physical properties of the matrix resin.

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

The extender pigment has an average particle size of 5 to 25㎛, can 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 invention, the extender pigment and the conductive material may be used in amounts of 30 to 70% by weight and 0.001 to 0.1% by weight, respectively, based on the total weight of the epoxy resin portion (A). .

According to one embodiment of the invention,

The epoxy resin portion (A) is 10 to 50% by weight, preferably 20 to 40% by weight, sieving pigment 30 to 70% by weight, preferably 40 to 60% by weight, 1 to 5% by weight of the 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 of reactive diluent containing an epoxy group, preferably 7 to 12% by weight Containing,

The epoxy curing agent portion (B) is 30 to 80% by weight of epoxy curing agent (amine resin), preferably 40 to 70% by weight, 10 to 40% by weight of non-reactive diluent, preferably 15 to 35% by weight, and curing accelerator 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-component coating composition for an antistatic epoxy flooring comprising the following steps:

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

(1b) an epoxy resin portion (A) is prepared by adding and mixing an epoxy resin, an additional sieving pigment, a pigment component and an additional reactive diluent to the wet grinding mixture obtained above, and

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

The present invention is explained in more detail below.

In general, epoxy resins can be widely used in various applications in combination with suitable curing agents. Epoxy floor coating composition's excellent adhesion to concrete is recognized as a major advantage, and it is suitable for use in high-performance paints due to its low shrinkage and mechanical and chemical resistance compared to other types of paints to protect concrete. .

Epoxy flooring systems that are currently commercialized can be classified into two types, solvent type and solventless type. As the solvent type, a thin film type (about 300 μm dry film thickness) to apply rollers twice a month and a top coat and a solvent-free top coat of a solvent type after coating a thick film (about 2000 μm or more dry film thickness) using a squeegee or the like. There is a thick film to paint once roller. In the case of the solvent type has a problem that it is harmful to the air pollution and workers' health as a large amount of volatile solvent is used in order to obtain a good coating film, such as roller workability, leveling. In addition, the solvent type requires at least two coatings in order to obtain a coating film of at least 200 μm in order to have a function as a flooring material due to the characteristics of the solvent type paint having a low solids content ratio. This usually requires one day of drying at room temperature for repainting once, which leads to an increase in working periods and man-hours of at least two days.

On the other hand, as said non-solvent type, there is a thick film type (self-leveling type) etc. which apply | coat 2000 micrometers or more using leki etc. In the case of the conventional solvent-free paints, not for roller painting, but for self leveling, the coating thickness should be 2000㎛ or more to form a good appearance. In order to supplement the physical properties of the solvent-based coating has to be uncomfortable.

This epoxy flooring is the most widely used as a flooring in many fields, but the development of the antistatic epoxy flooring is insufficient. Therefore, the technology of economically and effectively providing antistatic property to epoxy flooring is still an important technical problem, and many studies have been conducted until recently.

The present invention is a solvent-free two-component coating for antistatic epoxy flooring comprising an epoxy resin portion (A) comprising an epoxy resin, a diluent, a sieving pigment, and a conductive material and an epoxy curing agent portion (B) comprising an epoxy curing agent, a diluent, and a curing accelerator. The compositions, methods for their preparation, and the resulting antistatic epoxy floorings will be described in detail below sequentially.

(A) epoxy resin part

Solvent-free two-part coating composition for antistatic epoxy flooring of the present invention, wherein the epoxy resin portion (A) is 10 to 50% by weight epoxy resin, 30 to 70% by weight pigment, 1 to 5% by weight pigment component, and electroconductivity. 0.001-0.2% by weight of material, and 5-15% by weight of diluent.

Examples of the epoxy resin include bisphenol A type epoxy (DGEBA Type Epoxy), bisphenol F type Epoxy (DGFBF Type Epoxy), novalac type Epoxy, brominated epoxy, cycloaliphatic epoxy, and rubber modified. Epoxy (Rubber Modified Epoxy), Aliphatic Polyglycidyl Type Epoxy, Glycidyl Amine Type Epoxy, and BPA (Bisphenol A) and Epichlorohydrine (ECH) Bisphenol A type epoxy (DGEBA Type Epoxy) prepared by reacting may be specifically mentioned.

The extender pigments are not particularly limited and may be those commonly used as extender pigments in epoxy flooring, and generally 30 to 70% by weight, specifically 40 to 60% by weight, based on the total weight of the epoxy resin portion (A), Preferably it may 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, as inorganic particles, barium sulfate (precipitated barium sulfate, Baryte, etc.), aluminum silicate (clay, kaolin, bentonite, etc.), bone powder (talk ), Silica powder, diatomaceous earth, and the like, 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 invention, the extender pigments generally have an average particle size of 1 to 500 μm, specifically 5 to 25 μm, preferably 10 to 20 μm. According to a preferred embodiment of the invention, the extender pigment, in the resulting epoxy resin portion (A) or during its preparation, has an average particle size of generally 1 to 500 μm, specifically 5 to 25 μm, preferably 10 to 10 It may be selected from those that may be ground or have the above particle size to 20㎛.

When the particle size of the extender pigment in the wet grinding mixture is outside the above range (1 to 500 μm, specifically 5 to 25 μm, preferably 10 to 20 μm), the extender pigment particles crush the aggregates of the conductive material in the wet grinding process. And the effect of maintaining the dispersion of the pulverized nanoparticles is lowered, thus increasing the aggregates or insufficient dispersion.

According to one embodiment of the present invention, using calcium carbonate as the extender pigment may 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 having a particle size of 0.8 to 3㎛ can be used as a reinforcing filler, and ultrafine calcium carbonate having a particle size of 0.03 to 0.08㎛ can be used as a functional active filler. It may be included in an amount of 15% by weight.

In general, in the production of the coating composition, the lower the ratio of solid fillers such as extender pigments, the lower the thixotropy of the coating composition, so that the uneven finish due to roller coating cannot be obtained. It is known that it is difficult to form irregular patterns of constant size. Therefore, in selecting calcium carbonate, which is an extender pigment, it may be preferable to select and use a particle size in an appropriate ratio as in the ratio of using 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 is obtained by coating the surface of the extender pigment particle with fatty acids such as stearic acid, oleic acid, and glycerine. It can also raise the thixotropy to paint. At this time, the method of surface treatment of inorganic particles such as calcium carbonate as fatty acid, the fine particles calcium carbonate and fatty acids are mixed in a constant ratio to disperse high-speed so that each calcium carbonate particles are 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 giving a coloring effect, and can be selected and mixed with lead chromate salt, iron oxide, and the like, but is not limited thereto.

Generally, diluents are used to control viscosity decrease and solution flow, and mean components that remain in the cured product at the time of curing without being volatilized, unlike solvents. For example, benzyl alcohol and dibutylphthalate Non-reactive diluents such as DBP) and phenolic resins (nonyl-phenol). On the other hand, to dilute high viscosity epoxy resins based on bisphenol-A, bisphenol-F and novolacs and other polyurethanes and polymers such as reactive diluents selected from epoxy group-containing compounds are used.

Reactive diluents for use in the present invention are low viscosity epoxy group containing compounds having aliphatic or aromatic structures, for example glycidyl ethers or glycidyl esters having 1 to 3 epoxy groups. Typical examples of reactive diluents include mono-, di- or triglycidyl ethers of C ₆ to C ₁₄ monoalcohols or alkylphenols ; Monoglycidyl ether of cashew nut husk 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 cyclohexane dimethanol ; Triglycidyl ether of trimethylolpropane ; And glycidyl esters of C6 to C24 carboxylic acids or mixtures thereof.

Alternatively, as specific examples of glycidyl ethers or glycidyl esters having an aliphatic or aromatic structure and having 1 to 3 epoxy groups, n-butylglycidyl ether, aliphatic glycidyl ether, 2-ethylhexyl glycy Cydyl ether, phenyl glycidyl ether, O-cresyl glycidyl ether, nonylphenyl glycidyl ether, p-tertbutyl phenyl glycidyl ether, 1.4-butanediol diglycidyl ether, 1.6-hexanedioldi Glycidyl ether, neopentylglycidyl 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 eglycidyl ether, trimethylolpropene triglycidyl ether, glycerol polyglycidyl ether, Glycerol Polyglycidyl Ether, Penterritritol Polyglycidyl Ether, Kestol Glycidyl Ether, Serbitol Polyglycidyl Ether, Neokenoxy Acid Glycidyl Ether, Diglycidyl-1.2-cyclonucleic acid Carboxylate, diglycidyl-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 It is possible to use one or more reactive diluents selected from the group consisting of ethers, but is not limited thereto.

In the present invention, an epoxy group-containing compound such as low viscosity glycidyl ether or a derivative thereof can 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), Cardura ™ E10 (Hexion) and the like can be exemplified.

As carbon nanotubes (CNT, Carbon Nanotube) that can be used 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 may include fullerene, graphene, nanowires, nanorods, and the like. Carbon nanotubes 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) Used in content.

(B) epoxy curing agent part

In the solvent-free two-component coating composition for antistatic epoxy flooring of the present invention, the epoxy curing agent portion (B) may include 10 to 40% by weight of an epoxy curing agent (amine resin) non-reactive diluent and 5 to 30% by weight of a curing accelerator. have.

The epoxy curing agent may be a polyamide classified as a modified aliphatic amine in the amine-based curing agent according to the chemical structure, and the diluent may be the above-mentioned non-reactive diluent benzyl alcohol and dibutylphthalate (DBP). ), Phenolic resin (nonyl-phenol), especially phenolic resin (dodecylphenol) can be used to control the final viscosity of the paint.

The epoxy curing agent portion (B) may further contain 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 preferably be selected from a carbon-based compound.

Generally, the solvent-free two-component coating composition for epoxy flooring comprising (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 more, and then cooled to room temperature ( After the component A) and component (B) have been reacted and cured, the composition is packaged by coating the surface with a thickness of 1,000 to 3,000 micron using a reiki or the like. At this time, for the curing reaction, (A) epoxy resin portion and (B) epoxy curing agent portion are mixed at a weight ratio of 5: 1, stirred at 1500 rpm for 5 minutes, and the components (A) and (B) are mixed within the pot life. Packaging by Laura's painting can be completed within the maximum time available).

(C) Production method of two-part coating composition

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

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

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

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

In 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, organic solvents or organic solvents commonly used in the paint field, for example, ethers, esters, alcohols, benzene, toluene, kerosene and the like can be used as the organic medium.

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

In the step (1b), the amount of the wet grinding mixture, the epoxy resin, the calcium carbonate, the pigment component, and the reactive diluent, which is the extender pigment, is not particularly limited, and in the resultant epoxy resin portion (A), the epoxy resin 10 to 50% by weight, preferably 20-40% by weight, calcium carbonate 30-70% by weight, preferably 40-60% by weight, pigment components 1-5% by weight, preferably 1-4% 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 reactive diluent, preferably 7 to 12% by weight.

In the step (2), the epoxy curing agent (amine resin), the non-reactive diluent and the curing accelerator, in the resulting epoxy curing agent part (B), 30 to 80% by weight, preferably 40 to 70, of the epoxy curing agent (amine resin) 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, preferably 5 to 25% by weight of the non-reactive diluent. In some cases, the additive can 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 the extender pigment and the conductive material in the above-mentioned step (1a), the organic pigment selected from the reactive diluent, the extender pigment such as calcium carbonate and the conductivity such as carbon nanotubes It can be obtained in the form of a homogeneous mixture by adding the material and wet grinding using a ball mill or the like. The above-mentioned extender pigment may be selected from materials having an average particle size of approximately 5 to 25 μm or having the average particle size after wet grinding.

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

According to one variation of the present invention, the mixing and dispersing of the extender pigment and the conductive material may be promoted or assisted by ultrasonic grinding or the like.

In general, carbon-based conductive materials such as carbon nanotubes have low dispersibility with organic materials such as organic solvents, and thus are used in large amounts, or surface modified or modified, in order to obtain a paint composition having satisfactory antistatic properties. Or by using a special dispersing method or dispersing aid. However, conductive materials such as carbon nanotubes, fullerenes, and graphenes are economically disadvantageous because they are more expensive than other conductive materials such as carbon black, graphite, and metals. Methods of increasing acidity or using other special dispersing or dispersing agents are also economically disadvantageous as additional costs are incurred.

In the present invention, when expensive conductive materials such as carbon nanotubes, fullerenes, and graphene are used in the form of a sieving pigment such as calcium carbonate and a wet grinding mixture, excellent antistatic properties can be obtained even when the conductive materials are contained in a very small amount. There is an advantage that can be represented.

One of the advantages of the present invention is to use carbon-based nanoparticles, such as carbon nanotubes, fullerenes, and graphenes as conductive materials, and thus to conductive materials (eg, carbon black, graphite, conductive metals, etc.) that are used in the prior art. In spite of being used in a very small amount or a small amount, it shows excellent antistatic property and wear resistance.

Another advantage of the present invention, because the amount of the conductive material is very small, solve the problem of the gloss stain according to the roller pattern, the high wear resistance due to the high PVC%, and the durability of the epoxy lining to improve the durability of the user It can increase satisfaction.

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

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 produced.

Another advantage of the present invention is that since the coating composition is manufactured in a solvent-free two-part type, it is excellent in long-term storage, and it is easy to apply not only rollers or spray coatings but also paints using rake or hera, and thus excellent workability. to be.

Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited only 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 were gradually added under stirring, followed by further stirring for 5 minutes at 1000 rpm and 30 minutes at 1500 rpm. . The resulting mixture was ground with a sand mill at 3,000 rpm until the dispersion particle size of calcium carbonate became 20 µm, and 35 parts by weight of the reactive diluent was further added to adjust the viscosity to prepare a carbon nanotube paste.

(1b) Preparation of Epoxy Resin Part (A):

In the cylindrical reactor, 30 parts by weight of an epoxy resin (DER331, Dow Chemicals), 3 parts by weight of butylglycidyl ether as a reactive diluent, 0.4 part by weight of Disperbyk-110 (wetting dispersant), BYK, an antifoaming 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, a sieving pigment, 0.4 parts by weight of carbon nanotube paste obtained in step (1a), and 15.6 parts by weight of non-reactive diluent, were further added at 1,200 rpm. Time dispersion was carried out to prepare the epoxy resin portion (A).

(2) Preparation of Epoxy Curing Agent Part (B):

In the cylindrical reactor, 50 parts by weight of the amine resin (Jeffamine D230), 40 parts by weight of the non-reactive diluent (dodecylphenol, hydrocarbon-based) and 10 parts by weight of the curing accelerator (DMP-30) were added, and stirred for 1 hour to epoxy. The hardener part (B) is manufactured.

Example 2

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

Comparative Example 1

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

Comparative Example 2

In the step (1a) of Example 1 using an epoxy resin in an amount of 50 parts by weight instead of a reactive diluent, without using calcium carbonate, the amount of the reactive diluent is changed from 35 parts by weight to 48.5 parts by weight to prepare a carbon nanotube paste The procedure was the same as in Example 1 except for the above.

Reference Example 1

The procedure was the same as in Comparative Example 1 except that the 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 components used in Examples, Comparative Examples and Reference Examples and their contents are described. Table 2 below is to prepare a flooring using the two-component epoxy coating composition obtained in Examples, Comparative Examples and Reference Examples, and to measure and describe the appearance and antistatic properties of the resulting flooring.

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 μm) - - 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 to 10 ⁸ 10 ^{7-10 10} 10 ^{10-10 11} 10 ⁹ to 10 ¹⁰ Coating smoothness Good usually Bad Bad Bad

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

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

For reference, when the CNT paste containing excess carbon nanotubes was not prepared but first mixed with an epoxy resin to prepare an epoxy resin portion (A) (Reference Example 1), a trace amount of carbon nano The antistatic property was worse than the case where a tube was used. These results, in the present invention can be used to achieve excellent dispersion effect of carbon nanotubes using calcium carbonate, whereby the flooring material of the present invention can have an excellent antistatic effect even if containing a small amount of carbon nanotubes Indirectly prove that.

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

Claims (8)

Solvent for antistatic epoxy flooring comprising an epoxy resin portion (A) comprising an epoxy resin, a reactive diluent, a sieving pigment and a conductive material, and an epoxy curing agent portion (B) comprising 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㎛, can 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,
The extender pigment and the conductive material are used in the form of a wet milling mixture wet milled in a liquid organic medium, solvent-free two-component coating composition for antistatic epoxy flooring.
The method of claim 1,
The epoxy resin portion (A) contains 10 to 50% 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 conductive material, and 5 to 15% by weight of reactive diluent. A solvent-free two-component coating composition for an antistatic epoxy flooring, characterized in that.
The method of claim 1,
Antistatic, characterized in that the epoxy curing agent portion (B) comprises 30 to 80% by weight epoxy curing agent (amine resin), 10 to 40% by weight non-reactive diluent, 5 to 30% by weight curing accelerator and other carbon compounds Solvent-free two-part coating composition for an epoxy epoxy flooring material.
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, solvent-free two-component coating composition for antistatic epoxy flooring.
Method for producing a solvent-free two-component coating composition for an antistatic epoxy flooring according to claim 1, comprising the following steps:
(1a) Wet grinding of the extender pigment and the conductive material in a liquid organic medium to prepare a wet grinding mixture,
(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) An epoxy curing agent part (B) was prepared by mixing an epoxy curing agent, a non-reactive diluent and a curing accelerator.
The method of claim 5,
In the step (1a), 30 to 70% by weight of the extender pigment, 0.1 to 2% by weight conductive material, 25 to 50% by weight reactive diluent and 5 to 20% by weight additives, antistatic epoxy Method for producing a solvent-free two-component coating composition for flooring.
The method of claim 5,
The epoxy resin portion (A) obtained in the step (1b) is 20 to 40% by weight epoxy resin, 30 to 70% by weight sieving pigment, 1 to 5% by weight pigment component, 0.001 to 0.2% by weight conductive material and reactive diluent 5 It contains-15 weight%, The manufacturing method of the solvent free two-component coating composition for antistatic epoxy floorings.
An antistatic epoxy flooring prepared from the solventless two-part coating composition according to any one of claims 1 to 4.