TW502049B - Electrically conductive compositions and methods for producing same - Google Patents

Abstract

An electrically conductive composition and a method for producing same, for example by injection molding. The composition includes a matrix comprising substantially a first thermoplastic component, a second thermoplastic component having a higher polarity than that of the first thermoplastic component, the second component encapsulating a plurality of fibers forming a network of encapsulated fibers within the matrix, and a carbon component preferentially attracted to the second component so as to make said network an electrically conductive network within the matrix.

Description

Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 502049

5. Description of the Invention (1 Scope of the Invention The present invention relates to a conductive composition based on two thermoplastic compounds having different polarities, forming a mixture with glass fiber and carbon black, and / or carbon fiber, and a method for manufacturing the same. BACKGROUND OF THE INVENTION Conduction Polymer-based compositions are widely used in industrial applications, such as electrostatic discharge of plastic components, and plastic boxes that provide shielding of electromagnetic interference (EMI) for electronic components. Examples of electrostatic discharge (ESD) applications include electronic product packaging , Clean room equipment, storage containers, water carrier, wafer carrier and building construction in explosion-proof environment. &Amp; Compound specially designed for = electrical discharge, its typical surface resistance 値 is ι02 to 1013 ohm / squaire, The specific compounds for EMI shielding applications usually have a volume resistance of 10 · 2 to 10 2. The edge technology has polymer-based compounds that can have a suitable resistance suitable for electrostatic discharge and EMI shielding. A class of compounds known in the art is based on polypropylene or polyethylene with a carbon content of up to 40 to 60% by weight. Its surface resistance is about 10, 0hm / square. For EMI shielding applications, such polymers contain 30 to 50% PAN carbon fiber, 40% small aluminum sheet, 15% nickel-plated carbon fiber, or 5 To i 0% stainless steel fibers. The purpose of the method to increase the conductivity of polymers is to fill specific conductive additives such as metal powders, metal fibers, carbon black, carbon fibers, and recently used self-conductive polymer powders The behavior of this type of material is characterized by its extremely nonlinear electrical conductivity and filler concentration. When the filler contains _; _______________ _____-4-This paper size applies to China " ^ 票 准 (CNS) A4 ^ T ^ 297 17 (Please read the notes on the back before filling this page)

Employees' Cooperatives of the Central Standards Bureau, Ministry of Economic Affairs, Yinfan 502049 A7 ______B7 _— V. Description of the Invention (2) When the amount is low, the conductivity of the polymer compound is usually quite low, and the size is similar to the polymer matrix itself (10-16 to 10 -11 Ohm · 1 cnT1). As the content increases, the conductivity will suddenly rise in several small and large grades in a narrow concentration range, and then slowly rise to the conductivity of the concentrated filler powder itself, in the range of 10 to 10 "Ohm -1 cm 1. As shown by this behavior pattern, It is an insulator-conductor transition transition that occurs at a critical volume component (lower permeation limit). This lower limit occurs because a particle-like network structure is formed and extends throughout the entire sample volume, allowing current to begin to flow. U.S. Patent No. 4,169,816 discloses a conductive single thermoplastic raw material composition with high carbon content. The composition contains 15-30 parts of carbon black per 100,000 parts of polypropylene-polyethylene copolymer, 0.25 to 1 Parts of silicon oxide, and 1-10 parts of reinforcing fiber components selected from carbon fibers or a mixture of carbon fibers and glass fibers. US Patent No. 5,004,561 discloses another conductive composition based on a single thermoplastic with a high carbon content. Polyolefins, polyphenylene cyanide / acrylocyanine / phenylethyl cyanide / butadiene (ABS) copolymer resin, polybutylene terephthalate (PBT) resin, polybenzene For every 100 parts of thermoplastic resin selected from the ester and polyamine (PA) resin group, it contains 30-300 parts of conductive glass fiber, 5-40 parts of carbon black, and 5-40 parts of graphite. Russian Patent No. SU 1,643,568 No. discloses a high-carbon-based conductive thermoplastic composition which is obtained by dispersing carbon in a matrix to obtain conductivity. The composition includes 20-35% by weight of polypropylene, 10-20% by weight of polyamide, and 20-30% by weight of carbon. Black, 10-20% by weight graphite, and 15-20% by weight glass fiber. In this technique, there are two known methods for making conductive thermoplastic objects. -5-This paper size applies to China National Standard (CNS) A4 specifications ( 210 ^ 97 mm) " 一 -— (Please read the notes on the back before filling in this page)

V. Description of the invention (Method 3). Compression molding square black with a slow production rate requires the conductivity, Λ: =, which can be used with lower fillers (such as injection molding at a carbon production rate; method; most of the mechanical properties are not good. Fast Γ is formed with complex geometries, but the amount of conductive fillers required is large. One disadvantage of compression molding of conductive compounds is that they produce slow daggers: r »r 0. Compound-based compounds are used for electrostatic discharge and The main point of EMI shielding applications is that the formation of conductive polymer compounds requires a high proportion of conductive foods that 'causes high costs' and lacks processability and mechanical properties. At the same time, its high extinction and deficiencies are particularly unfavorable for clean room applications. Abstract The present invention provides an improved thermoplastic conductive composition. Dt According to a part of the present invention, the conductive composition includes a first thermoplastic component forming a continuous matrix and a second thermoplastic composition having a polarity higher than that of the matrix. The composition also includes fibers' in situ covered with a second thermoplastic component and forms a network structure in the matrix, and the carbon black component, which is adsorbed to the first component by its high polarity. The two components are better. The in-situ coated network structure containing carbon black, and its particles are located in a better position, can provide an electrical composition printed by the Consumer Cooperative of the Central Government Bureau of the Ministry of Economic Affairs. According to another aspect of the present invention In part, the ratio of the conductive carbon filler to the second component $ needs to be sufficiently high so that there is sufficient carbon filler on the interface between the second component and the matrix to provide conductive properties. Nevertheless, the overall carbon concentration is at least higher than that of the prior art The conductive composition is one grade smaller, so that the composition of the present invention has advantages in many applications including clean room applications. -6 This paper size applies to China National Standard (CNS) A4 specifications (210X297 mm 502049 Employees of the Central Standards Bureau of the Ministry of Economic Affairs Printed by the consumer cooperative A7 ____________ B7 _ V. Description of the invention (4) — ~ ^ A— The other purpose is to manufacture the thermoplastic conductive composition of the present invention by a rapid manufacturing method. The recent invention has been able to use injection molding When manufacturing a conductive thermoplastic composition, a low black concentration is used, and the mechanical properties of the composition are improved. The conductive composition of the present invention It contains a first thermoplastic component, a second thermoplastic component that has a higher polarity than the first thermoplastic component, and a second thermoplastic component that covers a large number of fibers to form a network structure inside the matrix. The carbon component of the second component is preferably adsorbed, so that the mesh structure becomes a conductive mesh structure in the matrix. In a preferred embodiment of the present invention, the first thermoplastic component is a composition with or without added elastomer. Parts of the polyolefin compound. The polyolefin compound is selected from the polypropylene group, which can be the same polymer or copolymer and polyethylene. The second component is polyamine or EVOH. A preferred specific example The composition contains less than 20 parts of polyamidoamine or EVOH per 100 parts of the composition. In another specific example, the first component is propionazine / butadiene / styrene and the second component is Polyamine or E vOH. In another specific example, the first component is selected from the group consisting of styrene, high-impact styrene and styrene oxide / polystyrene, and the second component is polyamine or EVOH. The carbon component of the composition of the present invention may be carbon black. Alternatively, the carbon component may interfere with the fibers, or may be used in combination. In a preferred embodiment, the composition contains less than 10 parts of carbon black per 100 parts. In another preferred embodiment, the composition contains less than 30 parts of carbon fiber per 100 parts. This paper is again applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page)

Patent Application No. 086116567 ^ Chinese Specification Correction Page (July 91) V. Description of the Invention (5) In a preferred embodiment, the composition has one or more volume resistance values ranging from about 0.1 to about 109 〇hm-cm, deflection coefficient to about 11,000 MPa, and tensile strength to 60 MPa. Brief description of the drawings The following detailed description in conjunction with the drawings will make the present invention more fully understood and understood, in which: FIG. 1 is a drawing illustrating the form of the conductive thermoplastic composition of the present invention; FIGs. 2A-2C are not A self-limiting injection molding composition of the present invention, the SEM micrograph of the frozen fracture surface (different magnifications); FIG. 3 is an exemplary block diagram illustrating a method for manufacturing the conductive thermoplastic composition of the present invention; FIG. 4 A-4 D are block diagram illustrations of 4 other manufacturing methods of the conductive thermoplastic composition of the present invention, with carbon black as the carbon compound; and Figures 5 A-5 C are 3 other conductive thermoplastic compositions of the present invention The block diagram of the manufacturing method demonstrates that carbon black and carbon fibers are used as the carbon compound. 0 Symbols of the graphic elements indicate the meaning of the symbols. 10 Conductive multi-component thermoplastic composition 12 Matrix (first thermoplastic component) 14 Glass fiber 15 Matrix Interface 16 Second thermoplastic component -8- This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) 502049 Patent Application No. 086U6567 Correction page (July 91) A7 B7 1 year 1 5. Description of the invention (Know 18 carbon black 3 1 Dry kneading step 3 2 Blending step 3 3 Melting and glass breaking fiber mixing step 34 Granulation step 3 5 Add Carbon fiber and carbon black step 36. Injection molding steps The detailed description of the present invention refers to FIG. 1. FIG. 1 is an exemplary edge view of the conductive multi-component thermoplastic composition of the present invention. The conductive multi-component thermoplastic composition is filled with a representative of 10- It includes a matrix 12 mainly formed of a first thermoplastic compound, a second thermoplastic compound 6 having carbon black shown in the micrograph of SEM in FIG. 2, and a glass fiber 14 coated thereon, as shown in FIG. 1. The glass fiber 1 4 is covered with black 2nd-8a. The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 502049 A7 B7 V. Description of the invention (6 Thermoplastic composition 16 coating, here Forms a conductive network structure within the polypropylene matrix 12. In a preferred embodiment, the first thermoplastic component is a polyolefin-based component, a 'phenylethyl fluorene (PS) -based component or acryl cyanide / styrene / butadiene ( Abs) trimer-based compounds, With or without an elastomer composition, the second thermoplastic component is a polyamidoamine (PA) or polyethylene acetol (evOH) copolymer. The elastomer component is preferably a combination of a plurality of elastomers. Adding elastomer to the compound can change the mechanical properties of the composition without seriously affecting its conductivity. Since the affinity of polyamide or EVOH 16 for glass fiber 14 is far more than for any first thermoplastic component, 〖〇 When the melt is kneaded, the second thermoplastic component is preferably covered with glass fibers 1 4 in situ as described in detail with reference to Figure 3 below, and a mesh group of coated fibers, In addition, the carbon black particles are adsorbed on the second thermoplastic component phase and are located on the second thermoplastic component (polyamide or ev0h) matrix interface as shown in reference number 15, which can make the coated fiber network. The structure can use far less carbon black than conventional technology, become conductive, and improve the mechanical properties of the composition, as described below. Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economics ~ Refer to Figures 2A and 2C—Electron scanning micrographs with different magnifications. The thermoplastic composition of the first phase is 16; The microstructure and the better carbon black 18 distribution are clearly visible. The second feature is Yiyi ’, because the composition 10 has a similar degree of electrical conductivity than in the past, and contains a very low concentration of carbon black. This is because the conductive carbon black particles form a continuous along the interface between the brother-thermoplastic component phase and the matrix (the first layer).

Wooden paper ruler Yan Caiguan (CNTTMii: (210X297, avFT 502049 No. 086116567 patent application Chinese manual revision page (July 91)

path. In addition, the carbon black particles are implanted in the amorphous phase of the second thermoplastic 16 (soaked in the second layer), which helps to generate conductive pathways. The network structure formed by the second thermoplastic component covering the glass fiber (soaked in the third layer) is more helpful. 3 to 5C, a preferred method for manufacturing the conductive thermoplastic composition of the present invention will be exemplified. Figure 3 is a general description, and Figures 4A-4C and 3A-5C respectively illustrate two other examples of non-self-limiting compositions. Figure 3 illustrates from left to right, in chronological order, a method including a compounding step 32, a pelletizing step 34, and an injection molding step 36. In a preferred embodiment, the blending step 3 2 includes dry kneading of the polypropylene resin shown in reference number 31 and the second thermoplastic component, and melting and mixing with glass fiber as shown in reference number 3 3, followed by Carbon fiber, carbon black, or both melted; ^ mixing and other steps. In the non-self-limiting example described below, the blending step 32 is performed in a twin screw compounder (Berstorf · Germany) at a processing temperature range of 200-2851 (corresponding to the melting point of the polymer component) and the screw speed is 55 rpm. The obtained product is granulated (step 34), and then sent to a three-cavity mold (strength rod, deflection rod, and drop-throw impact disk) containing American standard test materials (astm).

Battenfeld injection molding machine, injection molding at 200-285 ° C (step 36). Figures 4A-4D illustrate four preferred methods of manufacturing composition 10 in English, the composition of which contains carbon black as a carbon compound. Figure 4A-4D Description—Yu Ren 1 ΑΛ_ ^ 4 Non-limiting example of searching for I I 0 0 parts by weight polypropylene, 12 parts by weight polyamine, 30 parts by weight glass-breaking fiber, and 2 parts by weight carbon black composition 10 . Figure 4A shows a specific example of concentrated carbon black, such as reference number 37v, TF, Yushe -10-

502049 Patent Application No. 086116567 (Amended in July 91) B7 Five Inventions (8 ^)-added at the molding stage, not added at step 3 2 of the compounding, the resistance value is 537 Ohm-cm, The flexural modulus is 4819 soil 161 MPa. Figure 4B illustrates another method of dry kneading concentrated carbon black with polypropylene and polyamide. The obtained resistance value is 432 Ohm-cm and the flexural modulus is 4649 ± 32 MPa. Figure 4C illustrates that the concentrated carbon black is being mixed. Another method added at the time, the obtained resistance value is 2 14 Ohm-cm, and the flexural modulus is 4491 ± 5 1 MPa. In the specific example of Figure 4D, the glass fiber, polypropylene fluorene, and polyamide are dry-kneaded, and the concentrated carbon black is added during blending. The obtained resistance value is 43 1 Ohm-cm, and the flexural modulus is 3790 ± 63 MPa. . Figures 5A-5C illustrate three other preferred methods of making composition 10, which include carbon fibers or carbon black and finished fibers as carbon compounds. Figures 5A-5C illustrate an example of a non-limiting composition 10 comprising 100 parts by weight of polypropylene, 12 parts by weight of polyamide, 30 parts by weight of glass fibers, 2 parts by weight of black and 20 parts by weight of carbon fibers. Figure 5 A In another method, carbon black and carbon fiber are added in the injection molding step, which can obtain high conductivity (resistance value 0 · 465 Ohm-cm) and high flexural modulus (9770 ± 428 MPa) ° Figure 5 In another method of B, the carbon black is dry kneaded with polyfluorene and polyamide, as shown in step 39, which is different from the dry kneading of step 31 in other methods, and the carbon fiber is added during compounding (step 3 5). The obtained resistance value is 2 Ohm-cm, and the flexural modulus is 9550 ± 350 MPa. In another method of Fig. 5C, carbon fiber is added during blending, and the electrical ancestor is 8 Ohm-cm, and the flexural modulus is 8931 ± 267 MPa. This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210 X 297 cm) 502049 A7 B7 V. Description of the invention (9) From the above non-self-limiting specific examples and many changes resulting from this, specific methods can be selected for manufacturing The compound for injection molding of composition 10 changes the specific conductivity and mechanical properties of composition 10 (indicated by the above-mentioned flexural modulus). In all methods, the present invention provides a conductive thermoplastic composition capable of having high electrical conductivity and strong mechanical properties after injection molding. The following examples illustrate the invention without limiting it to certain scopes. All sample injection molding composition samples (12.6cm X 1.27cm X 0.32cm) are in accordance with ASTM D 257-93 and ASTM D 4496-87 methods, and Keithley instruments are used to measure the volume resistance and take its electrical characteristics. Silver paint is used to eliminate the contact resistance between the sample and the electrode. The mechanical properties are evaluated in accordance with ASTM test methods. Specifically, ASTM D 0638 is used to measure tensile properties, ASTM D 790 is used to measure flexure, ASTM D 256 is used to measure IZOD impact, and ASTM D 570 is used to measure water absorption. The glass fiber content and carbon black content in each sample were measured individually by ASTM D 5630-94 and ASTM D 1603-94. The composition morphology was studied by JEOL 5400 electron scanning microscopy. Take frozen junction fracture surface research. Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the notes on the back before filling this page) In the experiment, commercial grade PP (homopolymers and copolymers), ABS, PS, HIPS, NORYL (refer to Table 10- 13 details), PE (high density and low density grade), elastomer, PA (PA6, PA66, PA 11, PA12, PA 6 / 6.9, PA 6/12), EVOH, glass fiber (cut into short bundles, 3.2-6.3 mm long, 10-13 micrometer diameter), conductive carbon black and carbon fiber (cut into fiber segments, 6mm long, 7-8 micrometer diameter), etc. are used for research. A total of 5 carbon blacks were studied. Its -12- This paper is again applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 502049

7 B V. Description of the invention (10) The properties are listed in Table 1 below. Table 1 Properties Ketjen EC 300J (AKZO) Ketjoi EC 600JD (AKZO) Vulcan XC-72 (Cabot) Corax L6 (D ^ ussa) Conductex 975 (Columbian Chemical Company) Surface area BET, m2 / g 1000 180 265 250 Particle size, nm 30 29 18 22 Pore volume, ml / 100g 350 480 178 123 165 Surface area CTAB, m2 / g 480 86 150 153 Moth absorption, mg / g 900 1000 293 260 Volatile matter,% 0.5 0.6 1.0 1.5 1.0 pH 値 8 8 7. 7.5 7 (Please read the notes on the back before filling in this page) Γ All the proportions of the kneading ratio are weight, and each example is based on 100 parts by weight of the first compound. The conductive polyolefin composition includes: 100 parts by weight of a polymerizable matrix, 4 to 20 parts of polyamide, 10 to 55 parts by weight of glass fiber, 0.5 to 10 parts by weight of carbon black, and 0 to 30 parts by weight. Carbon fiber. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. Composition 10 Electrical and mechanical behaviors, with different polyamide blend ratios as a function of glass fiber concentration, polyamide / glass fiber ratio, and carbon black concentration. The resistance and mechanical properties of the composition function are summarized in Tables 2 A and 2 B. The samples here are in accordance with the manufacturing method of the present invention, that is, injection molding 0 -13- This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) 502049

A

7 B Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs

Table 2 Composition of Group A 1 2 3 4 5 6 7 8 9 10 Polypropylene (MFI 12) 100 100 100 100 100 100 100 100 100 100 100 Polyamide 6 5 5 5 5 5 8 8 10 12 10 Glass fiber (Vetro tex ) 12 12 20 20 20 20 30 30 30 30 carbon black (EC 600) 1 3 0.5 1 3 3 1 1.5 2 3 nature flexural modulus (MPa) 3044 3849 3041 3945 4104 4366 5003 4655 4941 5153 Izod impact indentation, J / m 69 64 33 83 60 57 76 75 79 65 Volume resistance ohm-cm > 108 3 · 3χ105 108 104 1.6χ105 8 · 6χ103 6.6χ103 3χ103 1.4χ103 6.5χ103 (Please read the precautions on the back before filling this page )

、 1T -14- This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) 502049 5. Description of the invention (12)

Table 2B Component 1 2 3 4 5 6 7 Polypropylene (MFI 25) 100 100 100 100 100 100 100 Polyamide 6 4 5.3 6.6 8 8 8 12 Glass fiber (Vetrotex) 20 20 20 20 20 30 30 Carbon black ( EC 600) 0.67 0.88 1.1 1.5 2 1.3 2 Specific gravity, Kg / dm3 1.02 1.01 1.02 1.02 1.02 1.06 1.06 Moisture absorption,% 0.04 0.06 0.06 0.04 0.05 0.08 0.08 Deflection coefficient, MPa 3984 3958 3954 3941 3936 4866 5039 Tension coefficient, MPa 54 58 52 52 58 63 63 Elongation at break,% 2.8 3.1 2.7 2.8 2.8 2.5 2.6 Izod impact, history, J / m 68 85 66 63 71 85 76 Melt flow power, 230Ό, 5.2 4 6 2.8 3 3.3 3.2 2.16Kg thermal deterioration temperature, ° c 161 163 161 162 163 164 163 volume resistance, Ohm-cm 3.24xl05 2.5xl03 3xl04 1.3xl03 7.9xl03 3.4xl03 1.2xl03 ( Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs, Tables 3A and 3B show the resistance and physical properties of different polypropylene / polyamide mixtures to glass fibers of composition 10 Dependency. The increase in tensile strength, coefficient and flexural modulus caused by the increase in glass fiber content is clearly visible. -15-This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297mm) 502049 7 Β Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (13)

Table 3 Composition of Group A 1 2 3 4 5 Polypropylene (MFI 12) 100 100 100 100 100 Polyamide 66 5 8 12 16 16.5 Glass fiber (Vetrotex) 12 20 30 40 50 Carbon black (EC 600) 1 1.5 2 2.8 2.8 Nature tensile strength, MPa 39.4 44 56.2 58 47.4 Elongation at break,% 3.2 2.6 2.3 2.1 2 Tensile coefficient, MPa 1771 2030 2634 3133 2406 Deflection modulus, MPa 3054 3801 4684 5394 5576 Izod impact, indentation, J / m 64 69 77 71 57 Water absorption,% 0.02 0.03 0.04 0.06 0.07 Specific gravity, kg / dm3 0.981 1.025 1.082 1.122 1.145 Volume resistance, Ohm-cm > 108 9.4xl04 4 850 440 2.3xl04 (Please read the (Please fill in this page again)

、 1T -16- This paper size applies to Chinese National Standard (CNS) A4 specification (210 × 297 mm) 502049 A7 B7 V. Description of invention (14)

Table 3B Group composition 1 2 3 4 5 6 7 8 9 Polypropylene (MFI 25) 100 100 100 100 100 100 100 100 100 100 Polyamide 66 4 5.3 6.6 8 8 6 8 10 12 Glass fiber (Vetrotex) 20 20 20 20 20 30 30 30 30 Carbon black (EC 600) 0.67 0.88 1.1 1.5 2 1 1.3 1.6 2 Specific gravity, Kg / dm3 1.02 1.00 1.01 1.04 1.02 1.05 1.06 1.05 1.06 Water absorption,% 0.04 0.04 0.07 0.04 0.05 0.05 0.07 0.1 0.05 Curvature factor, MPa 3917 3804 3858 3731 3936 4815 4640 4732 4856 Tensile strength, MPa 52 53 53 53 56 57 59 57 61 61 Elongation at break,% 2.7 3.1 3.0 3.0 3.0 2.6 2.4 2.9 2.0 Izod impact, indentation, J / m 64 71 76 66 67 75 75 77 62 Melt flow rate, 275 ° C, 18 12 11 8.6 11 8 8.8 8 6 2.16Kg Heat distortion temperature, ° c 161 163 163 162 162 164 165 165 163 Volume resistance, Ohm-cm 2xl 〇4 9.9x103. 4x103. 490 7.9x103. 650 814 241 175 (Please read the precautions on the back before filling this page).

, 1T Printed by the Consumer Cooperatives of the Central Standards Bureau, Ministry of Economic Affairs, Table 4 shows the resistance of the PP / PA / GF / CB system (100/12/3 0/4% combination ratio). For the second thermoplastic component (polyamide) ) Dependency. It is clear here that any type of polyamide can be used in the composition 10, and their conductivity can be determined by the degree of crystallinity of the selected polyamide. The composition 10 based on PA 66 and PA6, PA11, PA12 (semi-crystallized polyamidoamine) has a resistance lower than that of PA6 / 6-9 and PA 6-12 (amorphous polyamidoamine). Base. -17- This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210 × 297 mm) 502049 A7 B7 V. Description of the invention (15) At the same concentration of conductive additives, PA 66 (the most crystallized polymer in the study) Amine-based compounds can achieve a higher degree of electrical conductivity. Table 4 Properties PA66 PA 6 PA12 PA11 PA 6-6 / 9 PA 6-12 Tensile strength, MPa 58.4 54.2 51.9 49.6 58.5 56.6 Elongation at break,% 2.1 1.9 2 3 2.3 1.9 Tension coefficient, MPa 3256 3030 2541 1868 3074 3160 Modulus of curvature, MPa 4850 4699 4592 3899 4650 4890 Izod impact, indentation, J / m 72 70 68.8 58.9 61 62 Specific gravity, Kg / dm3 1.086 1.092 1.081 1.079 1.076 1.069 Volume resistance, Ohm-cm 700 3.3xl0 3 2 · 3x103 5.4xl03 3.3xl05 1.3xl05 It is also recognized here that any type of carbon black can be used in the composition 10. Table 5 shows a composition based on polyethylene terephthalate (100 parts), PA 66 (12 parts), and glass fiber (30 parts). It has five CB grades and two content levels, and various The electrical and mechanical properties of the composition. Looking at this table, it can be seen that the two most conductive carbon blacks, Ketjenblacks EC 300 and EC 600, provide the highest conductivity. (Please read the notes on the back before filling out this page) Order: -r Printed bags for employees' cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs -18 vertical This paper size applies to Chinese national standards (ci " s) A4 size (210X297 mm) 502049

7 B V. Description of the invention (16) Table 5 Properties EC600 EC 300 XC 72 CORAX L6 CONDU CTEX 2 phr 2 phr 4 phr 2 phr 4 phr 2 phr 4 phr 2 phr 4 phr Tensile strength, MPa 56.2 52.1 57.7 45.9 54 44.2 45.1 43.9 58.4 Elongation at break,% 2.1 2.5 2.3 2.6 2.3 2.6 2.2 3.1 2.1 Tension coefficient, MPa 3133 2776 2911 2087 2933 2291 2147 2193 3194 Flexural modulus, MPa 4684 4898 4803 4968 4747 5108 4335 4948 4638 Izod impact, indentation, 77-72 70 68 74 66 79 72 J / m Specific gravity, Kg / dm3 1.082 1.072 1.079 1.079 1.079 1.074 1.076 1.069 1.074 Volume resistance, Ohm-cm 850 1560 789 > io8 4110 > io8 852 > io8 4xl〇4 ( (Please read the notes on the back before filling out this page.) Another factor that determines the resistance and mechanical properties of the composition 10 is the fluidity (MF I) of the polymer matrix used. As clearly shown in Table 6 below, relatively low electrical resistance can be obtained using polypropylene such as higher MF I. Table 6 is as follows. t

kL Printed by the Employees' Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs -19- This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) 502049

7 B V. Description of the invention (17) · Table 6 Group composition 1 2 3 4 5 6 7 8 9 Polypropylene (MFI 3) 100 Polypropylene (MFI 12) 100 100 100 100 Polypropylene (MFI 25) 100 100 100 100 Polyamide 66 5 5 12 12 12 16 16 16.5 15 Glass fiber (Vitrotex) 12 12 30 30 30 40 40 50 50 Carbon black (EC 600) 1 1 2 2 2 2.8 2.8 2.8 2.5 Properties Flexural modulus, MPa 3054 3037 4168 4684 4450 5812 5515 5576 6249 Volume resistance, Ohm-cm ίο 7 2863 1100 850 290 565 405 2.3xl〇4 543 (Please read the precautions on the back before filling this page) The following Table 7 is provided as shown in Figure 5A- 5C, an example of a carbon fiber-containing composition 10. Carbon fiber / carbon black / glass fiber / second thermoplastic component (polyamide) / polyacrylamide compound can achieve a volume resistance of less than 1 ohm-cm. Table 7 below illustrates that the composition contains unlimited carbon fibers and their properties. Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs-20- This paper size applies to the Chinese National Standard (CNS) A4 (2 丨 0X297 mm) 502049 A7 B7 V. Description of the invention (18) Table 7 Group composition 1 2 3 4 5 6 7 8 9 10 Polypropylene (MFI25) 100 100 100 100 100 100 100 100 100 100 100 Polyurethane 66 12 12 12 12 12 14 14 14 14 14 Vetrotex 30 30 30 30 30 40 40 40 40 40 Carbon black (EC 600) 2 2 2 2 2 2.8 2.8 2.8 2.S 2.8 Carbon fiber 0 6 10 20 30 0 6 10 14 20 Properties Flexural modulus, MPa 4850 6264 7910 9770 10514 5964 6675 8129 9641 10495 Volume resistance, Ohm-cm 344 7.2 2 0.465 0.168 425 12.2 1.2 0.96 0.32 (Please read the precautions on the back before filling this page)

It is recognized here that the compounds of the present invention, especially those containing carbon fibers and having an electrical resistance below 1 Ohm-cm, can provide improved electromagnetic interference (EMI) at low carbon black and carbon fiber contents. Therefore, they have a wider range of uses than conductive plastics of the prior art, for example, in clean room applications where cleanliness carbon content is extremely important in manufacturing. It should be recognized here that the present invention is not limited by the foregoing content and various changes, and all persons within the scope of the present invention should exist. For example, although the present invention is described with reference to polypropylene, the present invention is equally applicable to other polyethylenes, #polyethylen and polyethylene-polyacrylamide mixtures. Polyethylene-based compositions are produced in the same manner as polypropylene, using ldpe and 腑 E grade '. As an example, 1 'a polyethylene terephthalate-based composition (! 00 parts on the same weight basis) and "part poly = (PA6)' 20 parts of glass fiber and 4 4 parts of carbon black (ec_)) kneader 'have 1 0 5-1 〇6 0hm_cm volume resistance. This paper size applies to China's CNS) A4 ^ m Order printed by the Central Consumers Bureau of the Ministry of Economic Affairs Consumer Cooperatives -21-502049 A7 B7 V. Description of the invention (19) Table 8 shows Two more polyethylene-based compositions. Table 8 Composition 1 2 PE 800 (MFI 20) 100 PE 600 (MFI 7) 100 Polyamide 66 12 12 Glass fiber (Vetrotex) 30 30 Carbon black (EC 600 ) 2 2 Specific gravity, Kg / dm3 1.07 1.07 Moisture absorption,% 0.06 0.06 Flexural modulus, MPa 1663 1622 Tension coefficient, MPa 746 678 Tensile strength, MPa 19.3 17.1 Elongation at break,% 3.0 3.3 Izod impact, pressure Trace, J / m 80 81 Melt flow rate, 275 ° C, 2.16Kg 33.2 18.8 Thermal deterioration temperature, ° c 96 96 Volume resistance, Ohm-cm lxlO6 2 xlO6 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please first (Read the notes on the back and fill out this page.) In other specific examples, The olefin component is replaced by another thermoplastic compound as the first component forming the matrix 12. In a fourth preferred embodiment, the first component forming the matrix 12 is propionazine / butadiene / benzene Ethylene (ABS), polystyrene (PS), high-impact polystyrene-22- This paper is sized to the Chinese National Standard (CNS) A4 (210X297 mm) 502049 A7 B7 V. Description of the invention (20) ( HIPS), and polyphenyl oxide / polystyrene (NORYL). Table 9 illustrates two examples of polyethylene-polypropylene-based compositions. Table 9 Composition 1 PE 800 (MFI 20) 100 PE 600 (MFI 7) 100 Polypropylene (MFI 25) 24 24 Polyamide 66 8 8 Glass fiber (Vetrotex) 20 20 Carbon black (EC 600) 1.5 1.5 Specific gravity, Kg / dm3 1.03 1.02 Moisture absorption,% 0.05 0.05 Flexure Modulus, MPa 1975 2117 Tension coefficient, MPa 1246 1176 Tensile strength, MPa 27 27.4 Elongation at break,% 2.3 2.5 Izod impact, indentation: J / m 68 70 Melt flow rate, 275 ° C, 2.16Kg 24.7 14.2 Thermal deterioration temperature, ° c 101 102 volume resistance, 0hm-cm 3xl05 3xl05 Printed by the Central Standards Bureau's Consumer Cooperative (please read the notes on the back before filling out this page) Table 1 0 indicates that it is formed by ABS, PS, HIPS and NORYL, and has a different second thermoplastic component (different types of polyamide composition ), Different glass fibers-23- This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) 502049 A7 B7 V. Description of the invention (21) Content and different low carbon black content (less than or equal to 3% ) 的 实施 例 10。 Composition 10 example. Table 1 0 Components 1 2 3 4 5 6 ABS 100 100 100 PS 100 HIPS 100 NORYL 100 Polyamide 6 12 12 Polyamide 12 8 12 12 Polyamide 66 12 Fiberglass (Vetrotex) 20 30 30 30 30 30 Carbon black (EC 600) 1.2 3 3 2 3 3 Properties Volume resistance, Ohm-cm 10S ίο 4 103 105 ΙΟ4 ΙΟ3 Table 1 1, 1 2 and 1 3 "J provides more PS, HIPS and NORYL as the base composition Paradigms, and their mechanical properties. Table 1 1 shows the dependence of the resistance and physical properties of PS / PA / GF / CB compounds on the glass fiber concentration. (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs -24- This paper size applies to China National Standard (CNS) A4 (210X297 mm) 502049 Printed by the consumer cooperative A7 B7 V. Description of the invention (22) Table 1 1 Group composition 1 2 3 4 PS (GP) 100 100 100 100 Polyamide 6 5 8 12 Polyamide 12 12 Glass fiber (Vetrotex) 12 20 30 30 Carbon black (EC 600) 1.5 2 3 3 Specific gravity, Kg / dm3 1.09 1.17 1.22 1.2 Moisture absorption,% 0.12 0.12 0.13 0.07 Flexural modulus, MPa 4850 5830 7100 7000 Tension coefficient, MPa 2740 3130 3650 3290 Tension Strength, MPa 56 70 66 59 Elongation at break,% 2 2 2 2 Izod impact, indentation, J / m 43 52 51 38 Melt flow rate, 23 (TC, 2.16 Kg 8.2 5.7 3.7 3.0 Thermal deterioration temperature, ° c 82 84-86 Volume resistance, ohm-cm 4.5 X 105 7.5 X 104 3.8 x 10 4 2.2 X 104 Table 1 2 shows the dependence of HIPS / PA / GF / CB compound resistance and physical properties on glass fiber concentration. -25- This paper Standards apply to Chinese National Standard (CNS) A4 regulations (210X297 mm) (Please read the back of the precautions to fill out this page)

502049 A7 B7 V. Description of the invention (23) Table 1 2 Group composition 1 2 3 4 HEPS 100 100 100 100 Polyamide 6 5 8 12 Polyamide 12 12 Glass fiber (Vetrotex) 12 20 30 30 Carbon black (EC 600 ) 1.5 2 3 3 Specific gravity, Kg / dm3 1.12 1.16 1.21 1.19 Moisture absorption,% 0.13 0.14 0.14 0.07 Flexural modulus, MPa 3600 4560 6140 6050 Tension coefficient, MPa 1800 2050 2630 2050 Tensile strength, MPa 43 51 61 46 Elongation at break,% 2 2 2 1 Izod impact, indentation, J / m 46 46 47 34 Melt flow rate, 230 ° C, 2.16Kg 2.3 1.7 1.9 1.7 Thermal deterioration temperature, ° c-97 92 93 Volume resistance , Ohm-cm 9xl〇6 7xl〇4 7 xlO3 1.5 χ 104 (Please read the precautions on the back before filling this page)

1T d Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Table 1 3 illustrates the dependence of the resistance and physical properties of NORYL / PA66 / GF / CB compounds on the glass fiber concentration. -26- This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 502049 A7 B7 V. Description of the invention (24) Table 1 3 Group composition 1 2 NORYL 100 100 Polyamide 66 12 16 Glass fiber (Vetrotex ) 30 40 Carbon black (EC 600) 3 4 Specific gravity, Kg / dm3 1.24 1.28 Moisture absorption,% 0.17 0.20 Flexural modulus, MPa 6501 7193 Tension coefficient, MPa 3382 4361 Tensile strength, MPa 64.1 79.2 Elongation at break ，% 2.0 1.8 Izod impact, waste mark, J / m 38 42 Melt flow rate, 275 ° C, 2.16Kg 1.0 0.5 Thermal deterioration temperature, ° c 122 124 Volume resistance, Ohm-cm 5 x10s 1.8 x 104 (please first (Please read the notes on the back and fill in this page again.) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs. Table 14 shows that the second thermoplastic component is a combination of EVOH and non-polyamide 10. This table shows the dependence of the resistance of PP / EVOH / GF / CB compounds on the glass fiber concentration. -27- This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 502049 A7 B7 V. Description of invention (25) Table composition 1 2 3 Polypropylene (MFI 25) 100 100 100 EVOH 8 10 12 Glass Fiber (Vetrotex) 20 30 30 Carbon black (EC 600) 2 2.5 3 Specific gravity, Kg / dm3 1.03 1.07 1.07 Moisture absorption,% 0.03 0.03 0.05 Flexural modulus, MPa 4530 5697 5529 Tension coefficient, MPa 2475 2572 2670 Tensile strength, MPa 59.7 62.1 61.8 Elongation at break,% 2.7 2.5 2.4 Izod impact, indentation: J / m 69 66 58 Melt flow rate, 230 ° C, 2.16Kg 5.0 4.5 3.2 Thermal deterioration temperature, ° C 160 160 160 volume resistance, Ohm-cm 1.7 xlO5 1.6 x 105 1.3 x 103 (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Central Standards Bureau, Ministry of Economic Affairs, Table 1 5 Description PP / PA / GF with elastomer / CB (PP: 60: 4 0 for elastomer) dependence of resistance and physical properties on glass fiber concentration. It is clear here that the compound containing elasticity can provide a car-crossing impact than the compound synthesized in Table 3B. -28- This paper size applies Chinese National Standard (CNS) A4g (210X297 mm) 502049 A7 B7 V. Description of the invention (26) Table 1 5 Group composition 1 2 3 4 Polypropylene 100 100 100 100 Polyamide 66 5 8 8 10 Glass fiber (Vetrotex) 12 20 25 30 Carbon black (EC 600) 1 1.5 1.5 2 Properties Flexural modulus, MPa 1500 1900 2000 2300 Izod impact, indentation, J / m 134 120 107 100 Surface resistance, Ohm / sq · 107 106 105 105 (Please read the notes on the back before filling out this page) Those skilled in the art should recognize that the present invention is not limited by the above specific description and description of the present invention. The scope of the present invention is only defined by the scope of the following patent applications: 4 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm)

Claims (1)

502049 No. 086116567 Patent Application Chinese Patent Application Amendment (May 91) AB 8 $ Iti —i—iILl VI. Application for Patent Scope (1. A conductive composition containing: substantially a first thermoplastic composition A second thermoplastic component having a higher polarity than the first thermoplastic component, the second component covering a large number of fibers to form a network structure of the coated fibers in the matrix; and It is preferably attracted to the carbon component of the second component so that the mesh structure becomes a conductive mesh structure in the matrix, and the carbon component is disposed at an interface between the second thermoplastic component and the matrix. In the meantime, the interfering component is carbon black and is present in an amount of less than 10 parts per 100 parts. 2. The composition according to item 1 of the scope of patent application, wherein the first thermoplastic component is with or without the addition Polyvinyl hydrocarbon compound of elastomer composition. 3. The composition according to item 2 of the scope of patent application, wherein the polyolefin is selected from the group consisting of polypropylene and polyethylene. 4. According to the scope of item 3 of the patent application Compound, wherein the polypropylene is a homopolymer or a copolymer. 5. The composition according to item 1 of the scope of patent application, wherein the second component is polyamine or EVOH. 6. According to item 5 of the scope of patent application Composition, wherein the composition contains less than 20 parts of polyamidoamine or EVOH per 100 parts. 7. The composition according to item 1 of the patent application scope, wherein the fiber is glass fiber. 8. According to the patent application scope The composition of 7 items, wherein the composition contains less than 55 parts of glass fiber per 100 parts. This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) 9. According to the scope of patent application! The composition of item, wherein the carbon component further comprises carbon fiber. 10. A composition according to item i of the application, wherein the carbon component is a mixture of carbon black and carbon fiber. 11. The composition according to item 9 of the scope of patent application, which contains less than 30 parts of carbon fiber per 100 parts. 12. The composition according to item 1 of the scope of patent application, which has a volume resistance from about 0.01 to about 10 Ohm-cm. 13_ According to the scope of patent application! The composition of item has a flexural modulus of up to about u.000 MPa. 14. The composition according to item} of the patent application, which has a tensile strength of up to 60 ”。. 15. The composition according to item i of the patent application, wherein the first component is selected from acryl cyanide / butyl Divorce / styrene, polystyrene, high-impact phenethylfluorene 'and polyphenyloxide / polyphenylethylfluorene. 16. The composition according to item 15 of the scope of patent application, wherein the second component is poly Amidine or EVOH. 17. The composition according to item 2 of the scope of patent application, wherein the elastomer component comprises a combination of elastomers. 18. The composition according to item 17 of the scope of patent application, wherein the combination of elastomers affects The composition has mechanical properties, but does not substantially affect its electrical conductivity. 19. A method of manufacturing a conductive composition, comprising combining a matrix substantially comprising a first thermoplastic component and a polarity higher than that of the first thermoplastic component -2-This paper size is in accordance with Chinese National Standard (CNS) A4 specification (21 × X 297 directors). 6. The scope of patent application for the second step of blending thermoplastic components. This second component is coated with a large number of fibers. To Forming a mesh structure covered with fibers in the matrix; and a carbon component preferably attracted to the second component, so that the mesh structure in the matrix becomes a conductive mesh structure, and the carbon composition Is set between the second thermoplastic component and the interface of the matrix, wherein the carbon component is carbon black and is present in an amount of less than 10 parts per 100 parts. 20. According to the method in item 19 of the scope of the applied patent, It further comprises the step of forming the first thermoplastic component from a polyolefin with or without an additional elastomer component. 21. The method according to item 20 of the application, wherein the polyolefin is selected from the group consisting of polypropylene and polymer. Ethylene. 22. The method according to item 21 of the patent application, wherein the polypropylene is a homopolymer or copolymer. 23. The method according to item 19 of the patent application, which further comprises forming the article from polyamine or EVOH. Steps of two thermoplastic components. 24. The method according to item 23 of the scope of patent application, wherein the composition contains less than 20 parts of polyamide per 100 parts. 25. The method according to item 19 of scope of patent application, wherein the Fiber The dimension is glass fiber. 26. The method according to item 25 of the patent application, wherein the composition contains less than 55 parts of glass fiber per 100 parts. 27. The method according to item 19 of the patent application, wherein the carbon component is separately Contains carbon fiber. -3- This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) 502049 ABCD 6. Application scope 28. The method according to item 19 of the application scope, where the carbon component is carbon black Mixture with carbon fiber. 29. The method according to item 27 of the application, wherein the composition contains less than 30 parts of carbon fiber per 100 parts. 30. The method according to item 19 of the application, wherein the composition has a volume resistance from about 0.1 to 109 Ohm-cm. 31. The method according to item 19 of the application, wherein the composition has a flexural modulus up to about 11,000 MPa. 32. The method according to item 19 of the application, wherein the composition has a tensile strength of up to 60 MPa. 33. The method according to item 19 of the scope of patent application, which includes forming the first part from propionazine / butadiene tau / styrene, polystyrene, high-impact polystyrene and polyphenyl oxide / polystyrene. A set of ingredients. 34. The method according to claim 33, wherein the second component is polyamide or EVOH. 35. The method of claim 19, wherein the elastomer component comprises a combination of elastomers. 36. The method according to item 35 of the application, wherein the combination of elastomers affects the mechanical properties of the composition and does not substantially affect its electrical conductivity. -4- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)