KR20140039456A - Bioplastic film containing conductive nanofiber layer of carbon black, and method for preparing the same - Google Patents

Abstract

The present invention relates to a bioplastic film having collected a conductive nanofiber including a carbon black, and to a method for preparing the same. According to the present invention, a conductive carbon black nanofiber can be manufactured, which has enhanced conductivity by adding an excellent carbon black, enables radiation at room temperature using electrospinning, and maintains high conductivity through a simple process. In addition, carbon dioxide can be reduced by collecting the conductive nanofiber into the bioplastic film and manufacturing the bioplastic film having biodegradability and conductivity, and environmental problems can be solved by minimizing environmental effects by being decomposed under natural state. [Reference numerals] (AA) Conductive nanofiber surface course; (BB) Bioplastic film layer

Description

Bioplastic film containing a conductive nanofiber containing carbon black and a method for manufacturing the same

The present invention relates to a bioplastic film and a method for producing the same, which collects conductive nanofibers containing carbon black having biodegradability and conductivity.

Plastic materials have been widely used in various moldings, packaging materials, industrial materials, consumer goods, etc. throughout the industrial field due to their excellent properties, various functions, and low prices, but these products are not decomposed naturally within a reasonable period of time. Environmental pollution caused by packaging waste generated after use rather than the original function is a serious social problem.

Conventionally, methods such as landfill, incineration, and recycling have been taken to treat such plastic wastes. Research is being conducted in various ways. In some developed countries, the practical use of decomposable plastics has already reached a considerable level.

Degradable plastics are bio-degradable plastics, which are largely degraded by microorganisms, enzymes, etc., and chemical bond cleavage due to photochemical and thermal reactions caused by solar radiation and solar radiation. Photo-degradable plastics that cause plastic decomposition by means of oxidation, oxidation-degradable plastics that cause plastic decomposition by oxidation reaction under the influence of temperature, and hydrolyzate that decomposes by hydrolysis reaction It may be classified as a hydrolytically-degradable plastic, and among these, research on biodegradable, photodegradable plastics or their complex degradable plastics is being actively conducted.

Among them, biodegradable plastics are attracting attention as the most environmentally friendly and efficient materials. Bioplastics are in the spotlight in terms of carbon dioxide reduction, but in addition, they have been pointed out as a disadvantage of biodegradable materials. This product has the advantage of overcoming the problems such as application limitations and (3) price competitiveness.

Bioplastics are plastics made by synthesizing high-molecular polyesters of microorganisms of hydrogen bacteria and nitrogen bacteria, for example, aliphatic polyesters produced by fermentation methods directly from starch, sugar, carbohydrates, vegetable oils or fats. It is made of resin. After a certain period of time after disposal, biodegradable properties of hard plastics are naturally decomposed by the decomposing elements emitted by microorganisms. Such bioplastics have a great advantage in that they are more environmentally sustainable materials than petrochemical-based plastics due to the use of bio raw materials. In particular, with regard to environmental protection and onset of climate warming, bioplastics are increasing in importance not only in the packing sector but also in the manufacture of long-lasting industrial plastic products.

On the other hand, the existing conductive film is applied to the conductive material such as conductive polymer or carbon nanotube to the polymer material to manufacture the film and the method of applying the conductive material such as ITO, such as solution phase coating, printing method, deposition method, etc. This method has a disadvantage in that the price competitiveness is deteriorated due to the use of a large amount of expensive conductive materials.

Republic of Korea Patent Application No. 2010-0090329

Therefore, the inventors of the present invention intend to develop a conductive film that overcomes the disadvantages of the prior art, but the conventional method has given additional performance to the film by a method such as spraying, but in the present invention, a large amount of carbon black is nanofibers through electrospinning. It was confirmed that the conductivity is easily secured by connecting in a straight line within the present invention, and thus, the present invention was completed by preparing a bioplastic film in which conductive nanofibers containing carbon black were collected by applying this technique.

Accordingly, an object of the present invention is to provide a method for producing a bioplastic film in which conductive nanofibers containing environmentally friendly carbon black are collected.

Another object of the present invention is to provide a bioplastic film obtained by collecting conductive nanofibers containing carbon black prepared according to the method of the present invention.

In order to achieve the above object, the present invention comprises the steps of (a) preparing a carbon black polymer solution by dispersing carbon black in a polymer solution; (b) preparing a conductive nanofiber by electrospinning the polymer solution obtained in step (a); And (c) collecting the conductive nanofibers obtained in the step (b) on the bioplastic film. The method provides a method of manufacturing a bioplastic film containing conductive nanofibers containing carbon black.

In one embodiment of the present invention, after the step (a) may further comprise the step of further dispersing the carbon black polymer solution using milling or ultrasonic waves.

In one embodiment of the present invention, the content of the polymer in the step (a) may be added to 1 to 20% by weight based on the carbon black.

In one embodiment of the present invention, the polymer is polyethylene-vinylacetate (PE-VAc), polycaprolactone, polylactic acid, polyester, polyglycolic acid, polypropylene, polyethylene, polyhydroxyalkanoate , Polyvinylidene fluoride (PVDF), polyurethane (polyurethane), nylon, polyvinyl acetate (PVAc), polyvinyl alcohol (PVA), cellulose acetate can be selected from the group consisting of general polymers and copolymers thereof have. In one embodiment of the present invention, the carbon black may be Ketjen Black 300J or Ketjen Black 600JD.

In one embodiment of the present invention, the bioplastic film may be made of an aliphatic polyester resin prepared from a material selected from the group consisting of grain husks, grain bars or a mixture thereof as a natural raw material.

In one embodiment of the present invention, the solvent used in the preparation of the polymer solution in step (a) is toluene, chloroform, chloroform, dichloromethane, tetrahydrofuran, THF, methyl Ethyl ketone, methylpyrrolidinone (NMP), dimethyl sulfoxide (DMSO), dimethylformamide (DMF), methanol, ethanol, propanol, butanol, t- T-butyl alcohol, isopropylalcohol (IPA), benzyl alcohol, benzyl alcohol, ethyl acetate, butyl acetate, propylene glycol diacetate, propylene Glycol methyl ether acetate (PGMEA), acetonitrile (acetonitrile), trifluoroacetonitrile, ethylene glycol, dimethicone The acetamide (dimethylacetamide, DMAC) and at least one organic solvent or water is selected from the group consisting of acetone (acetone) can be used.

In one embodiment of the present invention, the electrospinning of the step (b) is spaced apart from the radiating portion and the laminated portion by 3.5 ~ 30cm at an applied voltage of 7.5 ~ 30kV, the flow rate of the polymer solution 0.001 ~ 10 mL per minute It can be carried out as.

In addition, the present invention provides a bioplastic film having conductive nanofibers containing carbon black at the surface layer and having electrical conductivity.

In one embodiment of the present invention, the diameter of the conductive nanofibers may be 50nm ~ 500um.

In one embodiment of the present invention, the conductive nanofibers may have a sheet resistance of 10 ¹ to 10 ⁸ Ω / SQ.

According to the present invention, carbon black nanofibers having conductivity have excellent electrical conductivity due to addition of carbon black having excellent performance, and are capable of spinning at room temperature using an electrospinning method and have a high electrical conductivity through a simple process. Nanofibers can be produced. In addition, by collecting the conductive nanofibers on the bioplastic film, a biodegradable and conductive bioplastic film may be manufactured to reduce carbon dioxide, and may be degraded in a natural state to minimize environmental impacts, thereby solving environmental pollution problems. In addition, by applying the conductive polymer fibers only to the surface layer, there is an effect that can reduce the cost while maintaining a high conductive function.

1 is a schematic diagram of a bio-based plastic that has collected nanofibers containing carbon black having electrical conductivity according to an embodiment of the present invention.
2 is a graph showing the measurement results of the sheet resistance of the nanofibers containing carbon black having electrical conductivity according to an embodiment of the present invention.
Figure 3 is a 1000 times and 5000 times scanning electron micrographs of nanofibers containing carbon black having electrical conductivity according to an embodiment of the present invention.

The present invention relates to a bioplastic film that has collected conductive nanofibers containing carbon black, and a method for manufacturing the same, to prepare conductive nanofibers containing carbon black that can maintain high electrical conductivity using an electrospinning process. It is characteristic in that the collected bioplastic film was produced.

The bioplastic film, which collects the conductive nanofibers containing carbon black prepared according to the present invention, maintains excellent conductivity and can reduce costs even though the conductive nanofibers are integrated on the surface in a multilayer structure. It has a characteristic structure consisting of a bioplastic film having sex.

The first aspect of the present invention is to provide a bio-plastic film made of carbon neutral natural resource industry by-product starch, manufacturing by-product octape (corn husk), rice by-product chaff as a raw material. Eco-friendly plastics are degradable plastics that are completely decomposed under the action of natural microorganisms such as light, heat, chemistry, bacteria, fungi and algae in their natural state, which can solve the packaging waste problem caused by the use of general purpose plastics Way.

A second feature of the invention is the use of an electrospinning process to produce conductive nanofibers. Electrospinning is an electrospinning process in which fibers are formed using electrical attractive force and repulsive force generated when the polymer solution or molten polymer is charged to a certain voltage. The electrospinning process can produce fibers of various diameters and can be applied to simple equipment and a wide range of materials. Through electrospinning process, it is possible to manufacture a film with high conductivity by using less raw materials than mass-use of expensive conductive material, which is a problem in the conductive film produced by coating, printing, and depositing existing conductive materials. have.

The third feature of the present invention is that a polymer made of a copolymer of the polymer component of the bioplastic is used as the polymer of the electrospinning solution in order to minimize peeling between the polymer included in the bioplastic film and the conductive nanofiber layer. Is in. Since the peeling of the film layer and the conductive nanofiber layer of the bioplastics lowers the reliability and the functionality of the product, a copolymer containing some polymers (eg, polypropylene, polyethylene, etc.) used in the bioplastic film layer (eg, polyethylene-poly By using a vinyl acetate copolymer), peeling can be prevented, and solution can be made into an electrospinning solution, and electrospinning can be made easy.

Accordingly, the present invention provides a method for producing a bioplastic film in which conductive nanofibers containing carbon black are collected.

In one embodiment, the method of manufacture of the present invention comprises the following steps.

Step 1: (a) dispersing carbon black in a polymer solution to prepare a carbon black polymer solution,

Step 2: (b) preparing a conductive nanofiber by electrospinning the polymer solution obtained in step (a),

Step 3: (c) collecting the conductive nanofibers obtained in the step (b) in the bioplastic film.

In the production method of the present invention, first, carbon black is dispersed in a polymer solution to prepare a carbon black polymer solution. In preparing the carbon black polymer solution, it is preferable to dissolve the polymer having the biodegradable fiber forming ability and the carbon black in an organic solvent. At this time, the organic solvent is toluene (toluene), chloroform (chloroform), dichloromethane (dichloromethane), tetrahydrofuran (tetrahydrofuran, THF), methyl ethyl ketone, methyl pyrrolidinone , NMP), dimethyl sulfoxide (DMSO), dimethylformamide (DMF), methanol, ethanol, propanol, butanol, t-butyl alcohol, isopropyl alcohol (isopropylalcohol, IPA) ), Benzyl alcohol, ethyl acetate, butyl acetate, butyl acetate, propylene glycol diacetate, propylene glycol methyl ether acetate (PGMEA), acetonitrile (acetonitrile), trifluoroacetonitrile, ethylene glycol, dimethylacetamide (DMAC) and acetone It can be used selected from the group, it may be used alone or mixed, but is not limited thereto.

It is preferable that it is 5,000-1,000,000, and, as for the average molecular weight of the said biodegradable fiber formation capability, it is more preferable that it is 10,000-300,000. Such polymers include polyethylene-vinylacetate (PEVAc), polycaprolactone, polylactic acid, polyester, polyglycolic acid, polyhydroxyalkanoate, polyvinylidene fluoride (PVDF), polyurethane , Nylon, polyvinylacetate (PVAc), polyvinyl alcohol (PVA), cellulose acetate and copolymers thereof may be selected and used, these may be used alone or in combination, but is not limited thereto.

The carbon black may be used as long as it is a general carbon black, preferably Ketjenblack 300J or Ketjenblack 600JD, but is not limited thereto.

In the present invention, the content of the polymer is preferably added to 0.1 to 50% by weight relative to the carbon black. If the amount is less than 0.1 wt%, the nanofibers are not formed or the mechanical properties of the fiber are significantly lowered. If the amount is added more than 50 wt%, the conductivity is very low.

In the production method of the present invention, the carbon black polymer solution may be further dispersed to further disperse the carbon black in the polymer solution. At this time, by performing a milling process using a ball mill or a bead mill, the carbon black may be dispersed in the polymer solution or additionally dispersed by ultrasonic grinding. And ultrasonic grinding may also be performed.

Next, the polymer solution is electrospun to produce conductive nanofibers, and the conductive nanofibers are collected on the bioplastic film. In one embodiment, using an electrospinning device, the conductive nanofibers are separated by separating the distance between the radiating part and the stacking part from 3.5 to 30 cm at an applied voltage of 7.5 to 30 kV and the flow rate of the polymer solution to 0.001 to 10 mL per minute. It can collect on a bio plastic film.

The bioplastic film is preferably made of an aliphatic polyester resin prepared from a material selected from the group consisting of grain husks, grains or mixtures thereof as a natural raw material.

Furthermore, the present invention provides a bioplastic film having electrical conductivity in which conductive nanofibers containing carbon black prepared by the above-described manufacturing method are collected on the surface layer.

The conductive nanofibers prepared in the present invention may have a diameter of 50 nm to 500 um, preferably 50 nm to 300 um.

In addition, the conductive nanofibers may have a surface resistance of 10 ¹ to 10 ⁸ Ω / SQ.

The bioplastic film according to the present invention has an advantage of reducing the cost while maintaining a high conductivity function despite the application of conductive nanofibers containing carbon black only to the surface layer.

According to the present invention, carbon black nanofibers having conductivity have excellent electrical conductivity by adding carbon black with excellent performance, and are capable of spinning at room temperature using an electrospinning method, and are capable of maintaining high electrical conductivity through a simple process. Nanofibers can be produced.

In addition, by collecting the conductive nanofibers on the bioplastic film, a biodegradable and conductive bioplastic film may be manufactured to reduce carbon dioxide, and may be degraded in a natural state to minimize environmental impacts, thereby solving environmental pollution problems.

Hereinafter, the present invention will be described in more detail with reference to Examples. It will be apparent to those skilled in the art that these embodiments are merely illustrative of the present invention and that the scope of the present invention is not limited to these embodiments.

< Example >

Bio-Based Plastic Film Manufacture of Carbon Fiber Containing Nanofibers

<1-1> Preparation of Carbon Black-Containing Polymer Solution

0.2 g of carbon black and a polyethylene-polyvinylacetate copolymer (Poly (ethylene-co-vinyl acetate)) (Sigma-Aldrich, 340502-250G, vinyl acetate 40 wt%) 0.5 g (Example 1), 1 g (Example 2) and 15 g (Example 3) were dissolved in 10 g of chloroform (Sigma-Aldrich, 288306-2 L), respectively, to prepare a carbon black polymer solution.

<1-2> Dispersion of Carbon Black in Polymer Solution

The polymer solution obtained in the step <1-1> was introduced into a ball mill process for 12 hours to uniformly disperse the carbon black and further disperse the carbon black particles in the polymer solution by using an ultrasonic mill. .

<1-3> Film production of carbon black nanofibers

The distance between the radiating part and the laminating part was 3.5 to 30 cm using the polymer needle obtained in the step <1-2> using an electrospinning device and a syringe needle having an applied voltage of 7.5 to 30 kV and a diameter of 0.1 to 3.0 mm. The biobase plastic film containing the conductive nanofibers containing carbon black was prepared by separating the polymer solution at a flow rate of 0.001 to 10 mL per minute.

< Experimental Example  1>

Surface Resistance Measurement of Carbon Black Nanofibers

In order to determine the sheet resistance of the carbon black nanofibers prepared in <Example 1> of the present invention, a four probe measuring instrument (DASOL ENG, FPP-RS8-1G, domestic) was used, and the analysis results are shown in FIG. 2. Shown in

2, the surface resistance of the carbon black nanofibers according to the present invention is 12kΩ / SQ (Example 1), 20kΩ / SQ (Example 2), 77 kΩ / SQ (Example 3), respectively, the content of the polymer It was found that the smaller the value, the smaller the resistance value.

The present invention has been described with reference to the preferred embodiments. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. Therefore, the disclosed embodiments should be considered in an illustrative rather than a restrictive sense. The scope of the present invention is defined by the appended claims rather than by the foregoing description, and all differences within the scope of equivalents thereof should be construed as being included in the present invention.

Claims (11)

(a) dispersing carbon black in a polymer solution to prepare a carbon black polymer solution;
(b) preparing a conductive nanofiber by electrospinning the polymer solution obtained in step (a); And
(c) collecting the conductive nanofibers obtained in the step (b) onto the bioplastic film, wherein the manufacturing method of the bioplastic film containing the conductive nanofibers containing carbon black is collected. The method of claim 1,
After the step (a) further comprising the step of further dispersing the carbon black polymer solution by using a milling or ultrasonic wave method for producing a bio-plastic film containing the conductive nanofibers containing carbon black. The method of claim 1,
In the step (a), the content of the polymer is a method for producing a bio-plastic film having conductive nanofibers containing carbon black, characterized in that the carbon black is added in an amount of 1 to 20% by weight. The method of claim 1,
The polymer is polyethylene-vinylacetate (PE-VAc), polycaprolactone, polylactic acid, polyester, polyglycolic acid, polypropylene, polyethylene, polyhydroxyalkanoate, polyvinylidene fluoride (PVDF) The conductive nanofibers containing carbon black are selected from the group consisting of polyurethane, nylon, polyvinyl acetate (PVAc), polyvinyl alcohol (PVA), cellulose acetate and copolymers thereof. Method of manufacturing bioplastic film. The method of claim 1,
The carbon black is ketjen black 300J or ketjen black 600JD characterized in that the conductive nanofibers containing the carbon nano-condensed bio-plastic film manufacturing method. The method of claim 1,
The bioplastic film is a natural raw material, the bioplastics containing the conductive nanofibers containing carbon black, characterized in that made of an aliphatic polyester resin prepared from a material selected from the group consisting of grain husks, grains or mixtures thereof. Method for producing a film. The method of claim 1,
The solvent used in the preparation of the polymer solution in step (a) is toluene, chloroform, chloroform, dichloromethane, tetrahydrofuran, THF, methyl ethyl keton, methyl Pyrrolidinone (N-methylpyrrolidinone, NMP), dimethyl sulfoxide (DMSO), dimethylformamide (DMF), methanol, ethanol, propanol, butanol, t-butyl alcohol, Isopropylalcohol (IPA), benzyl alcohol, benzyl alcohol, ethyl acetate, ethyl acetate, butyl acetate, propylene glycol diacetate, propylene glycol methyl ether acetate, PGMEA), acetonitrile, trifluoroacetonitrile, ethylene glycol, dimethylacetamide, DMAC) and acetone (acetone) using at least one organic solvent or water selected from the group consisting of carbon black containing conductive nanofibers, characterized in that the manufacturing method of the bioplastic film. The method of claim 1,
Electrospinning of the step (b) is carried out by separating the distance between the radiating part and the stacking part at 3.5 ~ 30cm at an applied voltage of 7.5 ~ 30kV, the flow rate of the polymer solution at 0.001 ~ 10 mL per minute A method for producing a bioplastic film in which conductive nanofibers containing black are collected. A bio plastic film containing conductive black fibers containing carbon black at the surface layer and having electrical conductivity. 10. The method of claim 9,
The diameter of the conductive nanofibers is 50nm ~ 500um, the bio plastic film containing the conductive nanofibers containing carbon black. 10. The method of claim 9,
The conductive nanofibers have a sheet resistance of 10 ¹ ~ 10 ⁸ Ω / SQ characterized in that the conductive bio-fiber film containing the conductive nanofibers containing carbon black.

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