阅读说明：本技术 一种导电阻燃聚氯乙烯复合材料及其应用 (Conductive flame-retardant polyvinyl chloride composite material and application thereof ) 是由 熊圣东 于 2021-08-06 设计创作，主要内容包括：本发明涉及一种导电阻燃聚氯乙烯复合材料及其应用。所述复合材料按重量份数计包括以下组分：聚氯乙烯树脂70份、氯化聚乙烯25～35份、稳定剂3～5份、增塑剂25～35份、阻燃剂5～8份、导电填料6～10份、改性树脂10～15份、润滑剂0.2～0.4份、其它助剂0.6～1份,所述的导电填料为镀银纳米石墨微片、镍包铜粉、单臂碳纳米管的混合物。本发明复合材料不仅具有高导电性,还具有高阻燃、高耐候、高力学性能和良好的柔软度特性,拥有广泛的应用领域,可以广泛用于导电包覆线、导电编织面料。(The invention relates to a conductive flame-retardant polyvinyl chloride composite material and application thereof. The composite material comprises the following components in parts by weight: 70 parts of polyvinyl chloride resin, 25-35 parts of chlorinated polyethylene, 3-5 parts of a stabilizer, 25-35 parts of a plasticizer, 5-8 parts of a flame retardant, 6-10 parts of a conductive filler, 10-15 parts of modified resin, 0.2-0.4 part of a lubricant and 0.6-1 part of other additives, wherein the conductive filler is a mixture of silver-plated nano graphite micro-sheets, nickel-coated copper powder and single-arm carbon nano-tubes. The composite material disclosed by the invention not only has high conductivity, but also has the characteristics of high flame retardance, high weather resistance, high mechanical property and good softness, has wide application fields, and can be widely applied to conductive covering wires and conductive woven fabrics.)

1. The conductive polyvinyl chloride composite material is characterized by comprising the following components in parts by weight: 70 parts of polyvinyl chloride (PVC) resin, 25-35 parts of chlorinated polyethylene, 3-5 parts of a stabilizer, 25-35 parts of a plasticizer, 5-8 parts of a flame retardant, 6-10 parts of a conductive filler, 10-15 parts of a modified resin, 0.2-0.4 part of a lubricant and 0.6-1 part of other additives, wherein the conductive filler is a mixture of silver-plated nano graphite micro-sheets, nickel-coated copper powder and single-arm carbon nano-tubes.

2. The conductive polyvinyl chloride composite material of claim 1, wherein the conductive filler comprises silver-plated nano graphite micro-sheets, nickel-coated copper powder and single-arm carbon nanotubes in a mass ratio of 1 (0.2-0.6): (0.05-0.1).

3. The conductive polyvinyl chloride composite material of claim 1, wherein the conductive filler comprises silver-plated nano graphite micro-sheets, nickel-coated copper powder and single-arm carbon nanotubes in a mass ratio of 1 (0.2-0.4): (0.05-0.08).

4. The conductive polyvinyl chloride composite material according to claim 1, wherein the mass ratio of the silver-plated nano graphite micro-sheets, the nickel-coated copper powder and the single-arm carbon nanotubes in the conductive filler is 1: 0.3: 0.07.

5. the conductive polyvinyl chloride composite material according to claim 1, 2, 3 or 4, wherein the mass content of nickel in the nickel-coated copper powder is 10-35%.

6. The conductive polyvinyl chloride composite material according to claim 1, wherein the chlorinated polyethylene is a resin type chlorinated high density polyethylene having a chlorine content of 20 to 35%.

7. The conductive polyvinyl chloride composite material according to claim 1, wherein the modified resin is a mixture of ethylene-vinyl acetate copolymer resin and vinyl chloride-vinyl acetate copolymer resin, and the mass ratio of the ethylene-vinyl acetate copolymer resin to the vinyl chloride-vinyl acetate copolymer resin is 1: (0.5 to 1.6).

8. The conductive polyvinyl chloride composite material of claim 7, wherein the vinyl acetate content in the ethylene-vinyl acetate copolymer resin is 10 to 30%, and the vinyl acetate content in the vinyl chloride-vinyl acetate copolymer resin is 10 to 30%.

9. Use of the conductive polyvinyl chloride composite material according to claim 1 in a conductive covered wire.

10. Use of the conductive polyvinyl chloride composite material of claim 1 in conductive woven fabrics.

Technical Field

The invention belongs to the technical field of high polymer materials, and particularly relates to a conductive flame-retardant polyvinyl chloride composite material and application thereof.

Background

The conductive composite material is a functional polymer material obtained by mixing a matrix resin with a conductive substance and processing the mixture by a resin material processing method. The method is mainly applied to the fields of electronics, electromagnetic wave shielding, integrated circuit packaging and the like, and has wide application prospects in the fields of light-emitting diodes, mobile phones, solar cells, miniature television screens, life science research and the like.

In the prior art, a composite method is often adopted when preparing a conductive resin material, namely, the conductive resin material is prepared by taking polymer resin as a matrix and carrying out combined action with conductive fillers, modified polymers or antistatic agents, wherein the conductive fillers are usually a large amount of conductive carbon black or metal powder and the like. For example, chinese patent application (cn201911284896.x), which relates to a polyvinyl chloride elastomer conductive composite material and a preparation method thereof, in the technology, a composite material prepared by using 32 to 50% by mass of conductive carbon black has general conductivity, and due to the addition of a large amount of conductive carbon black, the mechanical properties and processability of the material are greatly reduced. For another example, chinese patent application (CN201410812623.9) relates to a high-strength PVC conductive composite material and a method for preparing the same, and a large amount (15% to 18%) of carbon black and a traditional metal substance are also added to the technique as conductive fillers, and the material has a certain conductivity, but the material obtained by the method is a hard PVC material, and has poor processability, flame retardancy, weather resistance and other properties, and the application of the material is limited. For another example, chinese patent application (CN111234410A) relates to a polyvinyl chloride conductive material and a method for preparing the same, and the conductive composite material obtained by the technique has a certain flexibility, but the addition amount of the conventional conductive carbon black used reaches 10% -13%, the addition amount of the filler calcium carbonate is 7% -10%, the mechanical properties of the material are poor, and the material does not have a good flame retardant property, so that the application of the material is limited.

PVC materials with certain softness have wide application in the fields of films, cables, packaging materials and the like. However, PVC materials with softness generally contain plasticizers, and the addition of the plasticizers improves the processability of the materials and imparts softness to the materials, but also reduces the flame retardance, weather resistance, mechanical properties, self-cleaning performance and the like of the materials. In addition, in the preparation of the conductive PVC composite material, the addition of the low molecular weight plasticizer can greatly reduce the conductive effect of the traditional conductive filler (such as carbon black or metal powder). Therefore, the development of a high-conductivity flame-retardant polyvinyl chloride composite material with flame retardance, weather resistance, excellent mechanical properties and certain softness is a technical difficulty in the research of the current polyvinyl chloride composite material.

Disclosure of Invention

The invention aims to solve the problems in the prior art and provides a conductive flame-retardant polyvinyl chloride composite material which has good conductivity, weather resistance, flame retardance, certain softness and excellent mechanical property.

The purpose of the invention can be realized by the following technical scheme: the conductive flame-retardant polyvinyl chloride composite material comprises the following components in parts by weight: 70 parts of polyvinyl chloride (PVC) resin, 25-35 parts of chlorinated polyethylene, 3-5 parts of a stabilizer, 25-35 parts of a plasticizer, 5-8 parts of a flame retardant, 6-10 parts of a conductive filler, 10-15 parts of a modified resin, 0.2-0.4 part of a lubricant and 0.6-1 part of other additives, wherein the conductive filler is a mixture of silver-plated nano graphite micro-sheets, nickel-coated copper powder and single-arm carbon nano-tubes.

The volume resistivity of the composite material can be 10 by adding the conductive filler in the amount of 4.2 to 5.6 percent³The conductive composite material is in omega cm, and the conductive composite material has good flame retardance, weather resistance, flow processability and mechanical property.

In the conductive flame-retardant polyvinyl chloride composite material, the polymerization degree of the polyvinyl chloride resin is 950-1700.

In the conductive flame-retardant polyvinyl chloride composite material, the chlorinated polyethylene is resin type chlorinated high-density polyethylene with the chlorine content of 20-35%. The chlorinated high-density polyethylene used in the invention is a high polymer material prepared by chlorination substitution reaction of high-density polyethylene, has excellent weather resistance, ozone resistance, chemical resistance and oil resistance, and has good compatibility with PVC. The plasticizer is blended with PVC to obviously improve the mechanical and weather resistance of PVC materials, and can play a role in plasticizing PVC, so that the use amount of the plasticizer in the conductive flame-retardant polyvinyl chloride composite material is reduced, on one hand, the influence of the micromolecule plasticizer on the conductivity of the conductive filler is reduced, on the other hand, the plasticizer is flammable, and the flame retardant property of the material can also be improved by reducing the plasticizer amount. Moreover, the reduction of the amount of the plasticizer also reduces the risk of precipitation of the plasticizer in the composite material, and improves the easy cleaning performance of the material. In addition, the chlorinated high-density polyethylene contains a large amount of polar chlorine atoms, and the existence of the polar component increases the compatibility and the associativity of the matrix high polymer material, the conductive filler and the inorganic flame retardant, so that the uniformity of the composite material is enhanced, and the conductivity, the flame retardance, the weather resistance and the mechanical property of the material are perfectly presented.

In the conductive flame-retardant polyvinyl chloride composite material, the stabilizer is a calcium-zinc composite stabilizer. The calcium-zinc composite stabilizer can inhibit the decomposition reaction of polyvinyl chloride in light and heat environments.

In the above conductive flame-retardant polyvinyl chloride composite material, the plasticizer comprises one or more of dioctyl terephthalate, diisooctyl adipate, dioctyl sebacate, tri-n-butyl citrate, acetyl tributyl citrate, triethyl citrate, epoxy butyl stearate and trioctyl trimellitate. According to the invention, a certain amount of plasticizer is added into the conductive flame-retardant polyvinyl chloride composite material, molecules of the plasticizer can be inserted between PVC molecular chains, the mobility of the PVC molecular chains is increased, and the crystallinity of the PVC molecular chains is reduced, so that the plasticity and the flexibility of PVC are increased. The plasticizer is used together with chlorinated high-density polyethylene, so that the flow processing performance of PVC can be obviously improved, and the polyvinyl chloride composite material is endowed with good flexibility.

In the conductive flame-retardant polyvinyl chloride composite material, the flame retardant is antimony trioxide. Antimony trioxide is an additive flame retardant, and has no obvious flame retardant effect, but can show a synergistic effect in the presence of halide. The main resin materials in the system are polyvinyl chloride resin and chlorinated high-density polyethylene resin with the chlorine content of 20-35%, the molecular structures of the polyvinyl chloride resin and the chlorinated high-density polyethylene resin both have a large amount of chlorine elements, and the existence of the chlorine elements enables the matrix resin material to have certain flame retardant property. More importantly, in the high-temperature combustion process, chlorine elements in the polyvinyl chloride resin and chlorinated high-density polyethylene resin can react to generate high-concentration hydrochloric acid or free chlorine, the hydrochloric acid and the free chlorine can react with antimony trioxide to generate antimony trichloride or antimony pentachloride antimony chloride, the antimony compounds can reduce the contact of combustible substances and oxygen to generate a carbon covering layer, and free radicals in the combustion process can be captured in a gaseous state, so that the aim of high flame retardance by the addition of a low flame retardant is fulfilled, and the final composite material has good flame retardance and mechanical properties.

The chlorinated polyethylene in the invention has the plasticizing effect to reduce the using amount of the plasticizer, and the polar property of the polar chlorine element enables the chlorinated polyethylene to be used as a compatilizer to increase the compatibility between inorganic and metal materials and polymer resin, more importantly, the high chlorine content of the chlorinated polyethylene is matched with antimony trioxide to play a role in flame retardant synergy, so that the high flame retardant aim can be realized only by using the traditional antimony trioxide flame retardant without other flame retardant synergists, and the adding amount of the flame retardant is reduced.

In the conductive flame-retardant polyvinyl chloride composite material, the conductive filler is silver-plated nano graphite micro-sheets, nickel-coated copper powder and single-arm carbon nano tubes, and the mass ratio of the silver-plated nano graphite micro-sheets to the nickel-coated copper powder is 1 (0.2-0.6): (0.05-0.1) mixing the above components.

The conductive flame-retardant polyvinyl chloride composite material adopts silver-plated nano graphite micro-sheets as main conductive fillers. The graphite has small specific gravity, can use less addition amount under the same volume and has higher chemical stability; the nickel-coated copper powder has good conductive property and excellent electromagnetic shielding property, and has good conductive property when matched with the silver-plated nano graphite micro-sheet. The single-arm carbon nano tube is complementary to the conductivity of the silver-plated nano graphite microchip, and has ultrahigh conductivity and good mechanical and mechanical properties.

One of the most important features of the conductive polymer composite is that the more conductive particles are in contact, the denser the network is, and the smaller the gaps between the conductive particles are, the higher the conductivity of the composite is. In the invention, the silver-plated nano graphite microchip, the nickel-coated copper powder and the single-arm carbon nano tube have different crystal structures with the matrix resin, so that the silver-plated nano graphite microchip, the nickel-coated copper powder and the single-arm carbon nano tube as conductive particles can only stay and be embedded on a crystal boundary with a loose structure in the matrix. When the volume fraction of the conductive filler particles reaches a certain critical value, namely when the conductive particles embedded on the grain boundary are mutually contacted or the gaps are small, the potential barrier of the conductive filler particles is continuously reduced to form an electric percolation network, and a part of tunnel current channels with strong conductivity can be formed in a high-resistance phase, so that the conductive function is realized. When the single-walled carbon nanotube is embedded into a high polymer material matrix, a three-dimensional reinforced conductive network can be formed, and high conductive property is realized. In addition, the silver-plated nano graphite micro-sheet serving as the main conductive particle is microscopically a nano-scale sheet structure, and the structure is favorable for forming a conductive path in a polymer, so that the conductive percolation threshold of a composite material system can be greatly reduced, and the characteristics of low conductive filler addition and high conductivity can be realized. The addition of the low-conductivity filler reduces the cost of the conductive composite material, and greatly maintains the high-flow processability and good mechanical property of the material, so that the application field of the conductive composite material is increased. In addition, the silver-plated nano graphite micro-sheet is used as main conductive particles, ohmic contact is formed between different conductive particles, and no potential barrier exists on a contact surface, so that the resistance of electrons in the migration process is reduced, the migration rate of the electrons in the composite material is improved, and the conductivity of the composite material is improved. When the conductive filler is added into about 10 parts, the conductivity of the composite material reaches a certain value and does not change obviously with the increase of the dosage of the conductive filler, and the composite material has an obvious electric percolation phenomenon as the traditional conductive polymer composite material.

In addition, the silver-plated nano graphite microchip and the single-arm carbon nano tube can be combined with polar groups in PVC and chlorinated polyethylene under the coupling action of the vinyl acetate polar groups of the modified resin ethylene-vinyl acetate copolymer resin and the vinyl chloride-vinyl acetate copolymer resin, and a firm micro interface is formed among the components, so that the firm micro interface can effectively transfer destructive force to the silver-plated nano graphite microchip and the single-arm carbon nano tube when the composite material is damaged by external force, thereby greatly improving the mechanical properties such as tensile resistance, impact resistance and the like of the composite material and playing a role in reinforcing the mechanical properties. Within a certain addition range, the stronger the microscopic combination effect is, the stronger the mechanical property of the composite material is, with the increase of the parts of the silver-plated nano graphite micro-sheets and the single-arm carbon nano tubes. However, when the addition amount of the electric filler exceeds 10 parts, particularly 15 parts, the silver-plated nano graphite micro-sheets and the single-arm carbon nanotubes which have the reinforcing effect can generate agglomerated primary particles, the defect points are increased, the intermolecular force in the composite material is reduced, the capability of resisting the external destructive force is reduced, and the mechanical property of the composite material is reduced. The comprehensive judgment of the conductivity is combined, and the using amount of the conductive filler is controlled to be 6-10 parts.

Preferably, the conductive filler is silver-plated nano graphite micro-sheets, nickel-coated copper powder and single-arm carbon nanotubes in a mass ratio of 1 (0.2-0.4): (0.05-0.08) mixing the above components.

Further preferably, the mass ratio of the silver-plated nano graphite micro-sheets, the nickel-coated copper powder and the single-arm carbon nano tubes in the conductive filler is 1: 0.3: 0.07.

in the conductive flame-retardant polyvinyl chloride composite material, the mass content of nickel in the nickel-coated copper powder is 10-35%.

Preferably, the mass content of nickel in the nickel-coated copper powder is 15-30%.

In the conductive flame-retardant polyvinyl chloride composite material, the modified resin is a mixture of ethylene-vinyl acetate copolymer resin and vinyl chloride-vinyl acetate copolymer resin, and the mass ratio of the ethylene-vinyl acetate copolymer resin to the vinyl chloride-vinyl acetate copolymer resin is 1: (0.5 to 1.6).

The ethylene-vinyl acetate copolymer resin is formed by copolymerizing ethylene and vinyl acetate; the vinyl chloride-vinyl acetate copolymer resin is a polymer prepared by copolymerizing Vinyl Chloride (VC) and Vinyl Acetate (VAC) monomers. Both copolymer resins have polar and non-polar groups. The compatibility of the conductive filler, antimony trioxide and polyvinyl chloride resin is poor, and if the additive components cannot be uniformly dispersed in the continuous phase of the polyvinyl chloride resin, the conductivity, flame retardance, processing flowability and mechanical properties of the composite material are directly influenced. The ethylene-vinyl acetate copolymer resin, the vinyl chloride-vinyl acetate copolymer resin and the polyvinyl chloride resin have good compatibility, and the vinyl acetate polar group contained in the ethylene-vinyl acetate copolymer resin and the vinyl chloride-vinyl acetate copolymer resin can have a chemical coupling effect with the conductive filler, the antimony trioxide and other inorganic additives, so that the ethylene-vinyl acetate copolymer resin and the vinyl chloride-vinyl acetate copolymer resin have a compatibility effect on the matrix polyvinyl chloride resin and various inorganic additives, the flexibility, the toughness and the processing flow property of the composite material can be improved, and the composite material system is more uniform and reasonable. In addition, vinyl acetate groups in the ethylene-vinyl acetate copolymer resin and the vinyl chloride-vinyl acetate copolymer have good self-adhesive property, so that the polyvinyl chloride composite material has good thermal bonding property, and the smoothness and firmness of the structure can be improved by heat setting treatment after the polyvinyl chloride composite material is prepared into a covering thread woven fabric.

Preferably, the modified resin is a mixture of ethylene-vinyl acetate copolymer resin and vinyl chloride-vinyl acetate copolymer resin mixed according to the mass ratio of 1: 1.

Preferably, the vinyl acetate content in the ethylene-vinyl acetate copolymer resin is 10-30%, and the vinyl acetate content in the vinyl chloride-vinyl acetate copolymer resin is 10-30%. If the content of the polar vinyl acetate in the modified resin is too low, the function of compatible modification cannot be achieved; if the content is too large, the overall mechanical, conductive and heat-resistant properties of the composite material are reduced.

In the conductive flame-retardant polyvinyl chloride composite material, the lubricant can be ethylene bis-stearamide or oxidized polyethylene wax. Lubricants are a common additive for PVC composites in order to provide good processing flow properties, especially with inorganic filler systems. The lubricant used in the invention can increase the lubricating performance of the composite material and metal processing equipment and prevent the polyvinyl chloride composite material from being adhered to the processing equipment. On the other hand, the PVC melt is melted and then fused into the PVC melt, and the PVC melt plays roles in lubricating molecules and properly reducing friction in the melt, so that the PVC melt is convenient to process and mold.

In the conductive flame-retardant polyvinyl chloride composite material, the other auxiliary agents comprise 0.3-0.5 part of antioxidant and 0.3-0.5 part of anti-ultraviolet agent.

Preferably, the antioxidant can be one or two of hindered phenol antioxidant or phosphite antioxidant.

More preferably, the antioxidant can be one or more of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, tris (2, 4-di-tert-butylphenyl) phosphite, or ethyl 2,2' -thiobis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].

Preferably, the ultraviolet inhibitor is a benzophenone ultraviolet inhibitor.

Further preferably, the anti-ultraviolet agent comprises one or more of 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxybenzophenone or 4-dihydroxybenzophenone. As a woven fabric for a window, the fabric has good weather resistance, polyvinyl chloride is easy to decompose and age, and has a more sensitive chemical reaction to ultraviolet rays, and the polyvinyl chloride is easy to generate the chemical decomposition reaction under the irradiation of outdoor ultraviolet rays. The antioxidant added in the invention can effectively inhibit the oxidative decomposition of oxygen in the air on the PVC composite material, and improve the retention of physical properties of the composite material after the composite material is heated in the aerobic air. The anti-ultraviolet agent can absorb ultraviolet rays irradiated on a product so as to effectively inhibit chemical decomposition reaction between the ultraviolet rays and the PVC composite material, thereby ensuring the high weather resistance, ultraviolet resistance and other performances of the composite material.

The invention also provides a preparation method of the conductive flame-retardant polyvinyl chloride composite material, which comprises the following steps:

weighing 70 parts of polyvinyl chloride resin, 25-35 parts of chlorinated polyethylene, 3-5 parts of stabilizer, 25-35 parts of plasticizer, 5-8 parts of flame retardant, 0.2-0.4 part of lubricant and 0.6-1 part of other additives according to parts by weight, adding the mixture into a high-speed mixer for mixing, adding 6-10 parts of conductive filler and 10-15 parts of modified resin according to parts by weight when the temperature is increased to 100-120 ℃, continuously mixing for 1-5 min in the high-speed mixer, adding the mixed material into a cold mixer, cooling to 40-50 ℃, discharging, adding the cooled material into a double-screw extruder for plasticizing, melting, extruding and granulating, and granulating to obtain conductive flame-retardant polyvinyl chloride composite material granules.

The invention also provides an application of the conductive flame-retardant polyvinyl chloride composite material in a conductive covered wire.

The conductive coating line comprises a fiber layer and a conductive flame-retardant polyvinyl chloride composite material coating layer made of a conductive flame-retardant polyvinyl chloride composite material.

Preferably, the surface of the conductive flame-retardant polyvinyl chloride composite material layer of the conductive covered wire further comprises an electrostatic dust collector layer.

Preferably, the fiber can be any fiber, such as one or more selected from polyester fiber, glass fiber, acrylic fiber, polypropylene fiber, aramid fiber, spandex fiber and polyethylene fiber.

Preferably, the electrostatic dust collector layer is formed by coating an electrostatic dust collector solution on the surface of the coated wire and then heating and curing the coated wire, wherein the electrostatic dust collector solution comprises the following components in parts by weight: 8-12 parts of electrostatic dust collector, 10-15 parts of vinyl chloride-vinyl acetate copolymer resin, 0.1-0.2 part of dispersant and 50-70 parts of butyl acetate.

More preferably, the electrostatic dust collector is a mixture of calcium sulfide, ferroferric oxide, zinc stannate and magnesium hydroxide, and the mass percentages of the calcium sulfide, the ferroferric oxide, the zinc stannate and the magnesium hydroxide in the mixture are respectively 15-30%, 15-30% and 15-30%. When the quality of calcium sulfide, ferroferric oxide, zinc stannate and magnesium hydroxide is the same, the effect is best. Therefore, it is still more preferable that the mass ratios of calcium sulfide, ferroferric oxide, zinc stannate, and magnesium hydroxide in the electrostatic dust collector are all 25%.

The inorganic electrostatic dust collector used in the invention has poor compatibility with a high polymer resin material, and is difficult to have good compatibility with a PVC material layer in a cladding line. The invention introduces the vinyl chloride-vinyl acetate copolymer resin into the electrostatic dust collector solution, has good compatible coupling effect with the electrostatic dust collector (calcium sulfide, ferroferric oxide, zinc stannate and magnesium hydroxide) used by the invention, and simultaneously has good compatibility with PVC, so that the electrostatic dust collector coating can be better fused with PVC composite material into a whole, and the problems of poor compatibility of the electrostatic dust collector coating and the conductive coating line of the PVC base material and gradual reduction of electrostatic efficacy with time are solved, thereby the conductive coating line of the invention has long-term electrostatic adsorption efficacy.

The invention also provides an application of the conductive flame-retardant polyvinyl chloride composite material in conductive woven fabrics.

Preferably, the conductive woven fabric is woven by conductive coating wires, and each conductive coating wire comprises a fiber layer and a conductive flame-retardant polyvinyl chloride composite material coating layer made of a conductive flame-retardant polyvinyl chloride composite material.

Preferably, the surface of the conductive flame-retardant polyvinyl chloride composite material layer of the conductive covered wire further comprises an electrostatic dust collector layer.

Compared with the prior art, the invention has the following advantages:

1. the conductive flame-retardant polyvinyl chloride composite material disclosed by the invention has the advantages that the silver-plated nano graphite microchip, the nickel-coated copper powder and the conductive filler compounded by the single-arm carbon nano tube are matched with the polyvinyl chloride resin, the chlorinated polyethylene, the plasticizer, the modified resin, the flame retardant and the like to generate a synergistic effect, so that the composite material not only has high conductivity, but also has the characteristics of high flame retardance, high weather resistance, high mechanical property and good softness.

2. In the conductive flame-retardant polyvinyl chloride composite material, due to the reasonable adoption of the mutual synergistic effect of all systems, the conductive filler and the flame retardant can obtain good conductive and flame-retardant effects within 10 parts of the addition amount, the processable fluidity and the mechanical property retention of the material are greatly improved, and the material has wide application fields.

3. The conductive flame-retardant polyvinyl chloride composite material has good processability and softness, and can be widely used for conductive covered wires and conductive woven fabrics.

4. The conductive coated wire/conductive woven fabric has a conductive flame-retardant polyvinyl chloride composite material coating layer, is excellent in mechanical property, convenient to clean, excellent in weather resistance and very long in service life. The surface of the conductive coated wire/conductive woven fabric contains an electrostatic dust collector coating, and the dust collector can effectively adsorb tiny particles such as dust in the air by utilizing the electrostatic principle. The conductive coated wire of the invention can absorb certain PM2.5 even under the condition of no electrification because the surface of the conductive coated wire contains the electrostatic dust collector coating. The surface electrostatic dust collector coating can not gradually fall off along with the time, so that the conductive covered wire/conductive woven fabric has long-time electrostatic adsorption effect.

Detailed Description

The following are specific examples of the present invention and further describe the technical solutions of the present invention, but the present invention is not limited to these examples.

Example 1

Weighing 70 parts of polyvinyl chloride resin with the polymerization degree of 1100, 30 parts of chlorinated high-density polyethylene with the chlorine content of 32%, 4 parts of calcium-zinc composite stabilizer, 30 parts of dioctyl terephthalate plasticizer, 6 parts of flame retardant antimony trioxide, 0.3 part of ethylene bis stearamide, 0.4 part of antioxidant tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 0.4 part of ultraviolet-resistant agent 2-hydroxy-4-n-octoxy benzophenone in parts by weight, adding the components into a high-speed mixer for mixing, and adding 8 parts of the components in parts by weight at the mass ratio of 1: 0.3: 0.07 silver-plated nano graphite microchip, nickel-coated copper powder (the mass content of nickel is 30 percent) and conductive filler of a single-arm carbon nano tube, then adding a mixture of 6.5 parts of ethylene-vinyl acetate copolymer resin with the vinyl acetate content of 25 percent and 6.5 parts of vinyl chloride-vinyl acetate copolymer resin with the vinyl acetate content of 15 percent, continuously stirring at a high speed for 3 minutes, then feeding into a cold mixer, cooling to 45 ℃, discharging, then adding into a double-screw extruder, plasticizing, melting, extruding, granulating, and pelletizing to obtain the conductive flame-retardant polyvinyl chloride composite material pellet.

Example 2

Weighing 70 parts of polyvinyl chloride resin with the polymerization degree of 1100, 25 parts of chlorinated high-density polyethylene with the chlorine content of 32%, 4 parts of calcium-zinc composite stabilizer, 35 parts of dioctyl terephthalate plasticizer, 6 parts of flame retardant antimony trioxide, 0.3 part of ethylene bis stearamide, 0.3 part of antioxidant beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate and 0.3 part of ultraviolet-resistant agent 2-hydroxy-4-methoxybenzophenone according to parts by weight, adding the components into a high-speed mixer for mixing, and adding 8 parts of the components in a mass ratio of 1: 0.3: 0.07 silver-plated nano graphite microchip, nickel-coated copper powder (the mass content of nickel is 30 percent) and conductive filler of a single-arm carbon nano tube, then adding a mixture of 6.5 parts of ethylene-vinyl acetate copolymer resin with the vinyl acetate content of 25 percent and 6.5 parts of vinyl chloride-vinyl acetate copolymer resin with the vinyl acetate content of 15 percent, continuously stirring at a high speed for 3 minutes, then feeding into a cold mixer, cooling to 45 ℃, discharging, then adding into a double-screw extruder, plasticizing, melting, extruding, granulating, and pelletizing to obtain the conductive flame-retardant polyvinyl chloride composite material pellet.

Example 3

The only difference from example 1 is that 10 parts by mass of a mixture of 1: 0.3: 0.07 silver-plated nano graphite microchip, nickel-coated copper powder (the mass content of nickel is 30 percent), and conductive filler of a single-arm carbon nano tube. The rest is the same as in embodiment 1, and will not be described again here.

Example 4

The only difference from example 1 is that 8 parts of antimony trioxide as a flame retardant was added to this example, and the rest is the same as example 1, and will not be described again here.

Example 5

The only difference from example 1 is that the chlorinated high density polyethylene added in this example has a chlorine content of 20%, and the rest is the same as example 1 and will not be described again here.

Example 6

The only difference from example 1 is that a mixture of 5 parts by weight of an ethylene-vinyl acetate copolymer resin having a vinyl acetate content of 25% and 5 parts by weight of a vinyl chloride-vinyl acetate copolymer resin having a vinyl acetate content of 15% was added in this example, and the other steps were the same as in example 1 and will not be repeated herein.

Example 7

The difference between the embodiment and the embodiment 1 is only that the conductive filler in the embodiment is added with 8 parts by weight of the following components in a mass ratio of 1: 0.2: 0.05 silver-plated nanographite microchip, nickel-coated copper powder (nickel content of 30% by mass), and conductive filler for single-arm carbon nanotube, the other steps are the same as those of example 1, and will not be described again here.

Example 8

The difference between this example and example 1 is only that the conductive filler in this example is added with 8 parts by weight of conductive fillers of silver-plated nano graphite micro-sheets, nickel-coated copper powder (nickel content of 30% by mass), single-arm carbon nanotubes in a mass ratio of 1:0.6:0.1, and the rest is the same as example 1 and will not be described again here.

Example 9

The comparative example differs from example 1 only in that 8 parts by weight of a mixture of 1: 0.3: 0.07 silver-plated nano graphite microchip, nickel-coated copper powder (nickel content is 5% by mass), and conductive filler of single-arm carbon nano tube. The rest is the same as in example 1.

Example 10

The difference from example 1 is only that in this example, 8 parts by weight of a mixture of 1: 0.3: 0.07 silver-plated nano graphite microchip, nickel-coated copper powder (the mass content of nickel is 40 percent), and conductive filler of a single-arm carbon nano tube. The rest is the same as in example 1.

Example 11

The only difference from example 1 is that in this example, a mixture of 6.5 parts of an ethylene-vinyl acetate copolymer resin having a vinyl acetate content of 5% and 6.5 parts of a vinyl chloride-vinyl acetate copolymer resin having a vinyl acetate content of 5% was added. The rest is the same as in example 1.

Example 12

The only difference from example 1 is that in this example, a mixture of 6.5 parts of an ethylene-vinyl acetate copolymer resin having a vinyl acetate content of 35% and 6.5 parts of a vinyl chloride-vinyl acetate copolymer resin having a vinyl acetate content of 35% was added. The rest is the same as in example 1.

Comparative example 1

This comparative example differs from example 1 only in that no conductive filler is added to the comparative example. The rest is the same as in example 1.

Comparative example 2

This comparative example differs from example 2 only in that the conductive filler in this comparative example is 8 parts of conductive carbon black. The rest is the same as in example 2.

Comparative example 3

The comparative example differs from example 1 only in that 4 parts by weight of a mixture of 1: 0.3: 0.07 silver-plated nano graphite microchip, nickel-coated copper powder (the mass content of nickel is 30 percent), and conductive filler of a single-arm carbon nano tube. The rest is the same as in example 1.

Comparative example 4

The comparative example differs from example 1 only in that 15 parts by weight of a mixture of, by weight, 1: 0.3: 0.07 silver-plated nano graphite microchip, nickel-coated copper powder (the mass content of nickel is 30 percent), and conductive filler of a single-arm carbon nano tube. The rest is the same as in example 1.

Comparative example 5

The comparative example differs from example 1 only in that 8 parts by weight of a mixture of 5: 3: 0.7 silver-plated nano graphite micro-sheet, nickel-coated copper powder (the mass content of nickel is 30 percent) and conductive filler of a single-arm carbon nano tube. The rest is the same as in example 1.

Comparative example 6

This comparative example differs from example 1 only in that 8 parts by weight of conductive fillers of silver-plated nanographite micro-sheets and nickel-coated copper powder (nickel content of 30% by mass) were added in a mass ratio of 1: 0.3. The rest is the same as in example 1.

Comparative example 7

This comparative example differs from example 1 only in that 30 parts of chlorinated high-density polyethylene having a chlorine content of 32% are replaced by 30 parts of high-density polyethylene. The rest is the same as in example 1.

Comparative example 8

This comparative example is different from example 1 only in that a mixture of 2.5 parts by weight of an ethylene-vinyl acetate copolymer resin having a vinyl acetate content of 25% and 2.5 parts by weight of a vinyl chloride-vinyl acetate copolymer resin having a vinyl acetate content of 15% is added thereto, and the rest is the same as example 1 and will not be repeated.

Comparative example 9

This comparative example differs from example 1 only in that 3 parts by weight of antimony trioxide, a flame retardant, was added in the comparative example. The rest is the same as in example 1.

Comparative example 10

The comparative example differs from example 1 only in that 8 parts by weight of a mixture of 1: 0.02 silver-plated nano graphite micro-sheet, nickel-coated copper powder (the mass content of nickel is 30 percent) and conductive filler of a single-arm carbon nano tube. The rest is the same as in example 1.

Application example 1

A conductive coated wire with the diameter of 0.33mm sequentially comprises a 220D polyester fiber layer and a conductive flame-retardant polyvinyl chloride composite material layer made of the conductive flame-retardant polyvinyl chloride composite material prepared in the embodiment 1 from inside to outside.

Application example 2

A conductive covered wire with the diameter of 0.35mm sequentially comprises a polyester fiber layer with the specification of 220D, a conductive flame-retardant polyvinyl chloride composite material layer made of the conductive flame-retardant polyvinyl chloride composite material of the embodiment 1 and an electrostatic dust collector layer from inside to outside, wherein the electrostatic dust collector layer is formed by coating an electrostatic dust collector solution on the surface of the covered wire and then heating and curing the electrostatic dust collector solution, and the electrostatic dust collector solution comprises the following components in parts by weight: 10 parts of electrostatic dust collector, 12 parts of vinyl chloride-vinyl acetate copolymer resin, 12 parts of dispersant BYK-1100.15 parts and 60 parts of butyl acetate, wherein the electrostatic dust collector is a mixture of 2.5 parts of calcium sulfide, 2.5 parts of ferroferric oxide, 2.5 parts of zinc stannate and 2.5 parts of magnesium hydroxide.

Application example 3

A conductive covered wire with the diameter of 0.35mm sequentially comprises a glass fiber layer with the specification of 300D, a conductive flame-retardant polyvinyl chloride composite material layer made of the conductive flame-retardant polyvinyl chloride composite material of the embodiment 1 and an electrostatic dust collector layer from inside to outside, wherein the electrostatic dust collector layer is formed by coating an electrostatic dust collector solution on the surface of the covered wire and then heating and curing the coated wire, and the electrostatic dust collector solution comprises the following components in parts by weight: 8 parts of electrostatic dust collector, 15 parts of vinyl chloride-vinyl acetate copolymer resin, BYK-1110.1 parts of dispersant and 70 parts of butyl acetate, wherein the electrostatic dust collector is a mixture of 2 parts of calcium sulfide, 2 parts of ferroferric oxide and 2 parts of magnesium hydroxide.

Application example 4

A conductive knitted fabric, which was knitted with the conductive covered wire in application example 1, and which had an open area ratio of 5%.

Application example 5

A conductive knitted fabric, which was knitted with the conductive covered wire in application example 2, and which had an open area ratio of 5%.

Application example 6

A conductive knitted fabric, which was knitted with the conductive covered wire in application example 3, and which had an open area ratio of 10%.

The performances of the conductive flame-retardant polyvinyl chloride composite materials prepared in the embodiments 1-12 and the comparative examples 1-10 of the invention are compared, and the comparison results are shown in table 1.

TABLE 1

Note: oxygen index test standard: GB/T5454-1997; test standard of color fastness to sunlight: GB/T8427-2008; volume resistivity test standard: GB/T1410-2006; the impact strength test standard GB/T1843-2008; tensile Strength test Standard GB/T16421-1996; shore A hardness test standard GBT 2411-.

The performances of the conductive covered wire prepared in the application examples 1 to 6 of the present invention and the woven fabric were compared, and the comparison results are shown in table 2.

TABLE 2

Breaking strength test standard: GB/T3923.1-1997; tear strength test standard: GB/T3917.2-2009; test standard of color fastness to sunlight: GB/T8427-2008

As can be seen from Table 1, the conductive flame-retardant polyvinyl chloride composite material prepared by the embodiment of the invention has good mechanical properties and weather resistance. Has good flame retardant property. The volume resistivity of the composite material is 10³The conductive property is achieved within the range of omega, and the conductive property of the optimized formula system is better. The hardness of Shao's A is about 92, and the product has flexibility.

As can be seen from the examples and comparative examples, as the content of the conductive filler playing a main conductive characteristic in the conductive flame-retardant polyvinyl chloride composite material decreases, the resistance of the prepared covered wire is larger, see examples 1 and 3 and comparative example 3; however, if the addition amount of the conductive filler is too high, the conductivity of the composite material is rather lowered, and an obvious electrical percolation phenomenon occurs, as shown in example 1 and comparative example 4. In comparative example 1 of the polyvinyl chloride composite material without the conductive filler, the prepared composite material was not conductive.

The ethylene-vinyl acetate copolymer resin and the vinyl chloride-vinyl acetate copolymer resin with the coupling and dispersing functions play an active role in the dispersion uniformity between the inorganic metal filler and the polyvinyl chloride resin in the system of the conductive composite material, so that the conductive and flame retardant functions can be fully exerted. If the content of the inorganic metal filler and the PVC filler in the formula is reduced, the dispersion uniformity of the inorganic metal filler in PVC is poor, the resistance of the material is increased, and the flame retardant property is weakened, as shown in examples 1 and 6 and a comparative example 8. If the content of polar vinyl acetate in the modified resin is not within the preferred range, the overall mechanical, electrical and thermal properties of the resulting composite material are reduced, see examples 1, 11 and 12.

The conductive filler used in the invention is 1 (0.2-0.6) by mass: (0.05-0.1), preferably, the conductive filler is a mixture of silver-plated nano graphite micro-sheets, nickel-coated copper powder and single-arm carbon nanotubes, and the mass ratio of the silver-plated nano graphite micro-sheets to the nickel-coated copper powder to the single-arm carbon nanotubes is 1: 0.3: 0.07. the conductive filler is preferably selected to have better conductive performance, as shown in examples 1, 7 and 8. If the mass ratio of the silver-plated nano graphite micro-sheets to the nickel-coated copper powder to the single-arm carbon nano tubes in the conductive filler is not 1 (0.2-0.6): (0.05 to 0.1), the resulting composite material was significantly poor in conductivity, as shown in example 1 and comparative examples 5 and 10. If an equal part of the conventional conductive carbon black is used in place of the conductive filler of the present invention, the conductivity of the resulting conductive material is significantly reduced, as shown in example 2 and comparative example 2. If the conductive filler does not contain the one-armed carbon nanotube, the conductivity of the resulting conductive material is also significantly reduced, see example 1 and comparative example 6.

In the nickel-coated copper powder of the present invention, the mass content of nickel is 10 to 35%, and if the mass content of nickel in the nickel-coated copper powder used is too small, the volume fraction of the conductive particles is reduced, which reduces the conductivity of the composite material, as shown in examples 1 and 9. If the mass content of nickel in the nickel-coated copper powder is too large, the conductivity of the composite material is also affected, and the examples 1 and 10 show.

In the invention, the silver-plated nano graphite micro-sheet and the single-arm carbon nanotube not only play a role in electric conduction, but also play a role in reinforcement, and the mechanical property of the composite material is increased along with the increase of the content of the silver-plated nano graphite micro-sheet and the single-arm carbon nanotube in a certain range, as shown in examples 1 and 3 and comparative examples 1, 3,5 and 6. However, if the added amount of the conductive filler is too high, the silver-plated nano graphite micro-sheets and the single-arm carbon nanotubes which have the reinforcing effect can generate agglomerated primary particles, the defect points are increased, the intermolecular force in the composite material is reduced, the capability of resisting the external destructive force is reduced, and the mechanical property of the composite material is reduced, which is shown in example 1 and comparative example 4.

The hardness of the composite material obtained by the invention is about 92, the hardness of the composite material is mainly determined by the content of the plasticizer and the compatibility of each system, and the hardness of the material is also influenced by the amount of the filler. If the plasticizer content is increased, the hardness is appropriately decreased, see examples 1, 2; if the content of inorganic or metallic fillers is reduced, the hardness thereof is suitably reduced, see example 1 and comparative examples 1, 3, 9; if the filler content of the system is increased, the hardness is increased, see example 1 and comparative example 4. In addition, if the system compatibility is poor, the filler is not uniformly dispersed, and the hardness of the resulting composite material is also increased, see example 1, example 11, and comparative example 8.

The composite material of the invention has good flame retardant property, and the flame retardant property is increased along with the increase of the addition amount of the flame retardant in a certain range, as shown in examples 1 and 4 and a comparative example 9. Similarly, the flame retardant performance of the material is related to the dispersion uniformity of the system, if the system compatibility is poor, the filler is not uniformly dispersed, and the flame retardant performance of the obtained composite material is reduced, as shown in example 1, example 11 and comparative example 8.

The polar chlorine element in the chlorinated high-density polyethylene used in the invention provides high flame-retardant synergistic effect on one hand, and can also increase the compatibility of inorganic and metal fillers and high-molecular resin on the other hand, if the chlorine content in the chlorinated high-density polyethylene used is lower or no chlorine element is contained, the overall properties of the material, such as flame retardance, electric conductivity and mechanical properties, are reduced, see examples 1 and 5 and comparative example 7.

From the application examples 1-6, the conductive flame-retardant polyvinyl chloride composite material can be successfully applied to conductive flame-retardant coated wires and braided fabrics thereof, and the obtained product has good mechanical property, flame retardance and weather resistance and also has a conductive characteristic.

The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.