KR20030089378A - Composition of the conductive polymer by using sodium chloride, and manufacture method thereof - Google Patents

Abstract

PURPOSE: A conductive polymer composition and its preparation method are provided, to obtain a polymer plastic material which is conductive, biodegradable and antibacterial and screens an electromagnetic wave. CONSTITUTION: The conductive polymer composition is prepared by mixing 20-99 wt% of a gel-phase base material, a thermoplastic resin, a rubber or starch with 1-80 wt% of a NaCl solution by a sol-gel method. The NaCl solution is prepared by dissolving 1-35.7 g of NaCl at a room temperature and 1-39.8 g of NaCl at a temperature of 100 deg.C to 100 g of water. The thermoplastic resin is selected from the group consisting of poly(vinyl chloride), polypropylene, acrylonitrile-butadiene-styrene resin, polycarbonate/acrylonitrile-butadiene-styrene resin, poly(methyl methacrylate), polyethylene, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, polycarbonate, nylon, low density polyethylene, high density polyethylene and crossline polyethylene; and the rubber is selected from the group consisting of styrene-butadiene rubber, butadiene rubber and ethylene-propylene rubber.

Description

Composition of the conductive polymer by using sodium chloride, and manufacture method

The present invention relates to a conductive polymer composition using sodium chloride, and to a composition and a method of manufacturing the same to have an electromagnetic shielding function, antibacterial function, and biodegradable function, and in particular, to shield the electromagnetic wave existing in the space to improve the unnecessary electromagnetic environment The present invention relates to a biodegradable composition and a method for producing the same, wherein the cause of infection by various bacteria is eliminated, and a polymer that does not rot well is rotted.

It is a situation that the peripheral device or the human body is adversely affected by the electromagnetic waves emitted or radiated from various electric / electronic products, wires, mobile communication base stations, broadcasting station antennas, transformers, etc. Among them, artificial organs, electronic devices, and automation are affected. There is a malfunction of the equipment, the human body is currently a controversial issue, but the results are not good in various animal tests.

Although there is an urgent need to develop electromagnetic wave removal and suppression products that protect peripheral devices and human body from such electromagnetic waves, products that are manufactured and sold in the form of single-sided sheets such as clothes, mats, and safety glasses manufactured using conductive materials are currently available. Grounding is essential. Manufactured by using a conductive material is more harmful because it is destroyed by the human body having a large amount of moisture when directly worn and used by humans due to the nature of electromagnetic waves.

The technique and the accompanying problems that have been proposed in the prior art for the removal of these electromagnetic waves will be described below.

First, metals (Fe, Cu, Ni, etc.) were added to plastics used for packaging to shield electromagnetic waves. This method requires heavy use of heavy metals, resulting in heavy product. Therefore, the package itself, which has high conductivity due to the use of excess metal, can avoid direct influence from electromagnetic waves by integrating or reflecting electromagnetic waves, but the grounding is essential because it is an open circuit from the concept of single-sided sheet, that is, electrical engineering. do. Therefore, when this is used as an electrical / electronic component package, integrated electromagnetic waves may flow into the electrical / electronic component, resulting in damage to the product. On the other hand, when using a small amount of metal, it is difficult to expect the electromagnetic shielding effect due to the non-connection between the metal materials.

Secondly, the manufacture of fibers that block electromagnetic waves by plating copper and nickel on polyester is a product that is in close contact with the human body due to high conductivity, and it is highly likely to shield electromagnetic waves through the human body when used.

Third, inorganic building board manufactured by adding ferrite (electromagnetic wave absorber) to inorganic materials (calcium silicate, gypsum-based, cement-based), or technology using electromagnetic wave absorber to add electromagnetic wave absorber to epoxy to manufacture printed circuit board In the case of a technique in which an electromagnetic wave absorber is added to the cable wire to absorb an electromagnetic wave, an excess electromagnetic wave absorber is added to reduce the economics and processability, and the electromagnetic shielding is possible in the high frequency band of the MHz region. It is not effective.

Fourth, conductive polymers, polyaniline, polypyrrole, and polythiopene, which have recently been in the spotlight, have many weak points. In particular, the disadvantage of weak heat resistance and dissolving in m-cresol or chloroform to use as a coating, casting or coating, the problem is that the solvent is a very harmful substance, the conductive polymer itself is difficult to use as an electromagnetic shielding agent is a conductive material Silver, graphite, and carbon black powders must be mixed and used, which is a double burden in economics.

In addition, products made of various polymers may become habitats and nutrients for various bacteria under a humid atmosphere or moisture, and various bacteria may be scattered therein. The prior art and its problems with respect to antibacterial that can protect the human body and peripheral products from various bacteria will be described below.

In the conventional antimicrobial technology, products commercialized by adding organic or inorganic antimicrobial agents to plastics (polyethylene, polypropylene, polyvinychloride, nylon, etc.), paints (epoxy, etc.), ceramics (tiles, tableware, glass), etc. It is commercialized in various fields such as paint. Organic antimicrobials can be expected to have antimicrobial effects in a short time, but they are expensive and require special care when in contact with the human body. Inorganic antimicrobials are less expensive than organics in the short term but can be expected to be human-friendly and long-term. And antimicrobial agents mainly for (-) bacteria are the mainstream.

Another object of the present invention is to look at the prior art and the problems associated with the biodegradability to rot well non-corrosive polymer well below.

As a raw material of biodegradable polymer products, grains such as starch or corn flour are finely pulverized and mixed with polymers, resulting in high price. However, biodegradability and antimicrobiality are in conflict with each other and there have been no reports on how to give two functions to the product at the same time. Therefore, based on the antimicrobial theory and biodegradability theory currently available, there is no way to pursue both simultaneously.

The present invention has been made to solve the above problems,

By developing a method capable of manufacturing non-conductive (insulating) polymer as a conductive polymer using sodium chloride, which is a natural material, a polymer composition capable of shielding electromagnetic waves is developed. Sodium chloride, a natural material used in this development, is environmentally friendly and harmless to the human body. It is easy to rot against polymers that are resistant to bacteria and antifungal properties due to its sterilizing power (antibacterial activity), and at the same time, it is difficult to rot in the long term. It is an object of the present invention to provide a composition having biodegradability. In addition, the present invention provides a multifunctional composition exhibiting many beneficial functions such as humidity control of the room by moisture absorption of sodium chloride.

Table 1 shows the electromagnetic wave measurement results.

Table 2 shows the antimicrobial measurement results,

Table 3 shows the antifungal measurement results.

Conductive polymer composition using a sodium chloride of the present invention and its preparation method for achieving the above object,

First of all, sodium chloride used in the present invention is naturally extracted from seawater or rock salt, and for industrial use, it is used as it is, but when used for food, it is usually recrystallized and purified. When collected from sea water, it is usually produced by salting method or by using ion exchange resin. In other words, neutralization of hydrochloric acid and sodium hydroxide produces a neutralization reaction in which sodium chloride (salt) and water are produced.

That is, sodium chloride is present as ions (Na +, Cl-) in the solution and solid sodium chloride is formed by evaporation of water. When mixed with water again, it exists as an aqueous solution containing the same ions as the left state of the reaction scheme (hereinafter referred to as brine), and sodium chloride in 100 g of water up to 1 to 35.7 g at room temperature and 1 to 39.8 g at 100 ° C. Melted to prepare salt water. Pure water, therefore, does not conduct electricity, but brine made from ionic materials such as sodium chloride (NaCl) is energized because it exists in the brine as ions such as NaCl (aq).

As described above, the present invention is characterized in that 1 to 80% by weight of brine prepared by dissolving sodium chloride in water is mixed with 20 to 99% by weight of thermoplastic resin, thermosetting resin, and rubber to form a conductive polymer.

In the compositions of the present invention;

In the case of the gel base material, thermoplastic resins (PVC (Polyvinychloride), PP (Polypropylene), ABS (Acrylonitrile Butadiene Styrene), PC (Polycarbonate) / ABS (Acrylonitrile Butadiene Styrene), PMMA (PolyMethlMethAcrylate), PE (Polyethylene), PE Polyethylene Terephthalate (PET), Polybuthylene Terephthalate (PBT), Polyphenylene Sulfide (PPS), Poly cabonate (PC), Nylon, Low Density Polyethylene (LDPE), High Density Polyethylene (HDPE), Crossline Polyethylene (XLPE) or Using any one of rubber [SBR (StyreneButadiene Rubber), BR (Butadiene Rubber), EPR (Ethylene Propylene Rubber)], starch,

The base material in the sol state may be formed of any one of thermoplastic resins [PVC Paste, PVA (Polyvinyl Alcohol), VAM (Vinyl Acetate Monomer), PPG (polypropylene glycol), Polyurethane blending of one or more materials, or thermosetting resin (epoxy). use.

The composition of conductive polymer and its manufacturing method by Sol (Gel) -Gel (Gel) method is to combine the resin which is a base material with salt water (sol state) to make conductive polymer in which sodium chloride is dispersed evenly on the surface of the base material and extrude it. And a sheet or a case through an injection process, and the Sol (Sol) -Sol (Sol) Method prepares a conductive polymer in a sol state by mixing salt water (sol state) at a predetermined ratio with a resin in which the base material is sol and sprays it. It maintains conductivity by coating the target product through the method or Knife coating equipment.

Below, it looks at a preferred embodiment of the present invention.

Example 1 PVC pellets selected from gelled thermoplastic resins or rubbers were impregnated with salt water containing 15% by weight of sodium chloride, followed by drying at 50 to 100 ° C to prepare PVC resin in which sodium chloride was dispersed on the surface. The conductive PVC resin prepared as described above was manufactured into a sheet through an extrusion process at 150 to 220 ° C., or a sheet was prepared by maintaining only fusion between the surfaces of the pellets. In the case of using PC pellets, the injection conditions were injected at a temperature range of 230 to 315 占 폚, a mold temperature of 50 to 120 占 폚, a screw speed of 30 to 115 rpm, and an injection pressure of 450 to 1150 kg / mm2.

[Example 2] In case of using PVC Paste selected from sol thermoplastic resin or thermosetting resin, 15 wt% of sodium chloride prepared was stirred to mix and disperse together, to prepare PVC Paste mixed with sodium chloride, and extrusion process The sheet was prepared through.

Example 3 In the case of using water in the initial manufacturing process, such as water-soluble paint or adhesive, after dissolving 1 to 20 weight of sodium chloride in 40 to 80% by weight of water in a hot water state (50 ~ 85 ℃), PVA (Poly Vinyl Alcohol) ) 4-10 wt%, AAC (Acrylic Acid) 0.3-0.8 wt%, Starch 7-14 wt%, VAM (Vinyl Acetate Monomer) 9-18 wt%, NP40 (Nonylphenol) 0.09 wt% and Dibutyl Phthalate (DBP) 0.3 to 0.8 wt% was added and stirred to prepare an adhesive in which sodium chloride was kept in an ionic state.

[Example 4] Fiber coating raw materials are two kinds of PUs having different modulus in polyurethane (PU) (PU 1; 25-31 wt% with modulus of 5-20, PU 2; 25-31 with modulus of 60-90 % By weight) and 9-15% by weight of acrylic toluene 10-15% by weight of solvent and 4-7% by weight of acetone 1-20% by weight of sodium chloride and 0.2-0.3% by weight of hardener, hard coal 4 to 7% by weight of CaCO ₃ , 9 to 15% by weight of paraffin chloride, 1.5 to 3% by weight of matting agent, and 0.4 to 0.7% by weight of silicon were foamed after foaming to prepare a foam product having conductivity.

Example 5 The compositions and products prepared as in Examples 1 to 5 are transparent. It was possible to produce a variety of colors by mixing additives that implement color as a way to give a sense of fashion. Particularly, when the black color is required, the electromagnetic shielding effect is further improved when the conductive carbon black is used together. The pigment amount used at this time was 0.1-10 weight%.

Looking at the working example of the present invention as described above;

[Example 1] The concept of electromagnetic shielding is

The conductive polymer composition and the product prepared through the composition and process as described above have high resistance (200 to 50000000 Ω) conductivity because the added sodium chloride is present in an ionic state in an aqueous solution. And even though water is evaporated to exist as sodium chloride in the product, the conductive polymer made of sodium chloride is able to be energized by absorbing moisture in the air due to the nature of containing moisture. As a result of measuring the electromagnetic wave shielding degree through the low frequency band breaker of TriField after coating the prepared composition on the cube, it can be seen that a significant amount of electromagnetic shielding effect. Table 1 shows the electromagnetic wave measurement results of the coated with conductive polymer layer (5-side coating, resistance: 3000-15000Ω / cm) in a 400mm × 400mm × 240mm box, where the measurement distance is the horizontal separation distance from the measuring device. The bottom surface refers to the vertical separation distance from the bottom surface with the measuring device.

In the case of the sheet form manufactured in the form of the existing single-sided sheet, if the ground is not grounded, the product made of the conductive material is more generated due to the nature of integrating electromagnetic waves. However, when the coating treatment with a conductive polymer made of a composition and a process of the present invention in a six-sided case as in the present invention, the conventional conductive material must be grounded unconditionally in a closed circuit rather than an open circuit. Experimental results show that the self-extinguishing system at different levels can be operated.

As shown in [Table 1], it was confirmed mechanically and visually that the electromagnetic wave was removed even when measured in the non-grounded state. This is a closed circuit concept. If the electromagnetic wave generated from the electromagnetic wave generation source is continuously integrated at one point of the present invention, the electromagnetic wave collected at this point circulates to the other point while the developed product is a conductive polymer with high resistance. Electromagnetic waves are reduced. However, in the open circuit, the collected electromagnetic waves are not cyclically moved, thereby increasing the amount of electromagnetic waves (this can be confirmed by the TriField measuring device). If the complete removal is not achieved in the ungrounded state due to excessive electromagnetic wave generation, for example, in the case of the stand lamp shown in [Table 1], a large amount of 450 V / m electromagnetic waves are generated in the untreated state, In the case of 400V / m is also reduced, in this case it can be seen that when the ground is reduced to almost 0V / m to 1V / m. Therefore, it may be better to ground, but as shown in the measurements, the result could be different from the existing concept of electromagnetic waves in the ungrounded state. In the case of adhesives, the grounding effect of the building surface can be maximized by the grounding property of the building surface, thereby maximizing the electromagnetic shielding effect. Even though the measurement targets in Table 1 are small, good results are obtained. In the case of a large area, the electromagnetic shielding effect is better.

Working Example 2 In terms of antibacterial properties,

Since sodium chloride used has both (+) and (-) ions at the same time in the brine state, the (+) ion component has antibacterial activity against (-) bacteria, and the (-) ion component has (+) bacteria. It has antibacterial ability. Therefore, the existing antimicrobial agent was able to exert an antimicrobial effect only for anionic bacteria due to the predominantly cationic substance, but the developed product exhibited antimicrobial effect in all bacterial regions.

And the results of the antimicrobial and antifungal measurement of the added sodium chloride weight are shown in [Table 2] and [Table 3], respectively. In the composition of the present invention, even about 5% by weight of sodium chloride, a composition showing 99.98% of antibacterial activity against antibacterial Escherichia coli and anti-mildew was obtained. The bacterium Bacillus subtilis showed positive antibacterial activity.

In this experiment, the antimicrobial test showed that the surface area of the specimen was 1 cm 2, and the bacterial fluid was measured after shaking culture (150 cycles / minute) at 25 ° C. for 24 hours, and the shake method was determined by Shake Flask method. For Escherichia coli, Escherichia Coli ATCC25922 was used. The antifungal test was assay ASTM G-21, test strain Aspergillus niger, Penicillium citrinum, Aureobasidium pullulans, Gliocladium virens, Chaetomium globosum, medium Potato-Dextrose Agar, incubation temperature 25 ± 2 ℃, measurement period was 3 weeks.

[Example 3] Biodegradability using sodium chloride,

Although antimicrobial and biodegradability are incompatible principles, even if there is a minute internal hole in a product such as a polymer sheet or PET used as a raw material for PET bottles, immersion in an aqueous solution of sodium chloride causes erosion into the polymer and causes degradability (Spannungsinstabilitaeten) bei der Kaltverformungs teilkristalliner Kunststoffes, Technische Universitaet Hamburg-Harburg, 1995). It can be seen that after preparing a high concentration aqueous solution of sodium chloride and putting the PET resin with concentrated holes, the resin part with holes melted and disappeared within two or three weeks. Therefore, the product made of sodium chloride can shorten the decomposition period of the existing polymers significantly.

Application examples of the present invention can be applied to various fields such as not only various interior and exterior materials of the building, but also housings, mats, sheets of semiconductors, antistatic sheets of semiconductor clean products, and packages.

In addition, although specific embodiments of the present invention have been described and illustrated above, it is obvious that the present invention may be variously modified and implemented by those skilled in the art.

Such modified embodiments should not be individually understood from the technical spirit or the prospect of the present invention, and such modified embodiments should fall within the appended claims of the present invention.

As described above, the composition of the present invention and the product using the same have excellent antimicrobial function as a natural material, unlike the conventional chemically treated oil or inorganic antimicrobial agent, while exhibiting an electromagnetic shielding effect even in a non-grounded state as a conductive polymer of high resistance. At the same time, it exhibits environmental friendliness like biodegradable materials.

Claims (3)

Gel base materials, thermoplastics (PVC (Polyvinychloride), PP (Polypropylene), ABS (Acrylonitrile Butadiene Styrene), PC (Polycarbonate) / ABS (Acrylonitrile Butadiene Styrene), PMMA (PolyMethlMethAcrylate), PE (Polyethylene), PET (Polyethylene) Terephthalate, Polybuthylene Terephthalate (PBT), Polyphenylene Sulfide (PPS), Poly cabonate (PC), Nylon, Low Density Polyethylene (LDPE), High Density Polyethylene (HDPE), Cross-Piece Polyethylene (XLPE)] or Rubber [SBR] (StyreneButadiene Rubber), BR (Butadiene Rubber), EPR (Ethylene Propylene Rubber) of any one of the materials, starch, 20 to 99% by weight, Electromagnetic waves characterized by mixing 1 to 80% by weight of the brine prepared by dissolving sodium chloride in 100 g of water to 1 to 35.7 g at room temperature and 1 to 39.8 g at 100 ° C by the Sol-Gel method. Masking, antibacterial and biodegradable functional compositions. The amount of the material used in any one of a sol base material, a thermoplastic resin (PVC Paste, PVA (Polyvinyl Alcohol), VAM (Vinyl Acetate Monomer), PPG (polypropylene glycol), polyurethane, or one or more of thermosetting resin (epoxy)) 20-99% by weight, Electromagnetic waves characterized by mixing 1 to 80% by weight of the brine prepared by dissolving sodium chloride in 100 g of water to 1 to 35.7 g at room temperature and 1 to 39.8 g at 100 ° C by the Sol-Sol method. Masking, antibacterial and biodegradable functional compositions. According to claim 1, Electromagnetic shielding, antimicrobial and biodegradable functional composition, characterized in that the composition of the pigment, in particular 0.5 to 10% by weight of conductive carbon black for black color.