WO2018036017A1 - Antistatic molding composition comprising conductive fiberglass, and method of preparing same - Google Patents

Antistatic molding composition comprising conductive fiberglass, and method of preparing same Download PDF

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Publication number
WO2018036017A1
WO2018036017A1 PCT/CN2016/108007 CN2016108007W WO2018036017A1 WO 2018036017 A1 WO2018036017 A1 WO 2018036017A1 CN 2016108007 W CN2016108007 W CN 2016108007W WO 2018036017 A1 WO2018036017 A1 WO 2018036017A1
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Prior art keywords
glass fibers
molding composition
conductive glass
conductive
antistatic
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PCT/CN2016/108007
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French (fr)
Chinese (zh)
Inventor
肖世英
黄骥
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五行科技股份有限公司
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Publication of WO2018036017A1 publication Critical patent/WO2018036017A1/en

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/04—Antistatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/53—Core-shell polymer

Definitions

  • the invention belongs to the field of polymer materials, and in particular relates to an antistatic molding composition comprising conductive glass fibers and a preparation method thereof.
  • Permanent antistatic agents such as MH2030 from Arkema, France, are special auxiliaries based on polyamide based on polyether segments. Generally, such antistatic agents are sensitive to environmental humidity, ie, high humidity and antistatic The effect is good, and vice versa; and such antistatic agents are not easy to color due to their own characteristics, it is difficult to make bright colors, or injection molding defects which are prone to weld lines during the injection molding process affect the appearance experience.
  • a material that uses carbon fiber to achieve a permanent antistatic effect because of the carbon fiber color limitation, the appearance of the product is black, and the color effect cannot be achieved. Therefore, it is necessary to develop a modified antistatic molding composition capable of achieving a permanent antistatic effect and being easily colored while satisfying various requirements of the product.
  • the present invention is directed to the deficiencies in the prior art, and provides a conductive glass fiber.
  • the present invention can be achieved by the following technical solutions:
  • the present invention provides an antistatic molding composition comprising conductive glass fibers, the composition comprising: 35 to 75% resin (A), 20 to 55 by weight percent % conductive glass fiber (B), 2 ⁇ 30% impact modifier (C), 0.5 ⁇ 30% flame retardant (D), 0.2 ⁇ 3% anti-drip agent (E), 0.05 ⁇ 1% lubricant (F) and 0.05 to 1% of the pigment (G), wherein the resin is a polycarbonate resin or a polyester carbonate resin.
  • composition of the present invention may further comprise optionally one or more additives such as 0.1 to 2% of an antioxidant, a heat stabilizer, a light stabilizer, a pigment, a mold release agent, a flow promoter, and the like.
  • additives such as 0.1 to 2% of an antioxidant, a heat stabilizer, a light stabilizer, a pigment, a mold release agent, a flow promoter, and the like.
  • the component A according to the present invention may be a single viscosity polycarbonate or polyester carbonate, or a polycarbonate or polyester carbonate of different viscosity, which can be transesterified, interfacially polymerized, solution polymerized, and bulk. Synthesis by polymerization or the like; the viscosity is related to the molecular weight of the component A, the concentration in the solution, and the temperature, wherein the average molecular weight of the polycarbonate or the polyester carbonate of a single viscosity or a different viscosity is selected from 45,000 to 90,000.
  • the component B conductive glass fiber of the invention is: the glass fiber substrate of the conductive glass fiber is pretreated to have good coating adhesion, and then the ruthenium doping is provided on the outer surface of the glass fiber.
  • Tin oxide conductive sol gel coating layer preferably, when the coating layer has a cerium mass content of 5 to 20% and the coating layer has a thickness of 2 to 5 um, the cerium-doped tin oxide coating layer can be uniformly distributed on the surface of the glass fiber
  • the conductive glass fiber has excellent electrical conductivity, transparency, high temperature resistance, oxidation resistance, radiation resistance, and is not limited by the climatic environment and the use environment, and is more durable; more preferably, it is blended in glass fiber and bismuth.
  • a nano silver coating layer is disposed between the tin oxide conductive sol gel coating layer, the nano silver coating layer has a thickness of 2-7 um; and the nano silver coating layer is disposed for the purpose of making the conductive effect stronger, and Nano A layer of antimony-doped tin oxide conductive sol gel coating layer is further provided on the basis of the silver coating layer in order to prevent the nano silver coating layer from falling off.
  • the component C impact modifier of the present invention may be a copolymer having a core-shell structure, which is a fine particle form composed of an elastomer core and at least one thermoplastic shell, and the particle size is generally 120 ⁇ . 550 nm;
  • the core of the above core-shell copolymer may be: isoprene, butadiene, alkyl acrylate, alkyl methacrylate homopolymer, silicone rubber elastomer, etc.
  • the shell of the copolymer is one or two or more compounds of styrene olefin, alkyl styrene, alkyl acrylate, alkyl methacrylate, or an aliphatic or aromatic vinyl compound containing a vinyl group.
  • Copolymers such as styrene, acrylonitrile, vinyl acetate, etc.; the core-shell copolymers have higher impact resistance, thermal decomposition temperature and better wear resistance than other impact modifiers.
  • a phosphate flame retardant such as benzenediol diphosphate, oligobisphenol A bis(diphenyl phosphate), phosphoric acid.
  • Tributyl ester or triphenyl phosphate has long-lasting flame retardant effect, good compatibility with other materials, water resistance, heat resistance and migration resistance.
  • the component E anti-drip agent of the present invention is a polytetrafluoroethylene (PTFE) anti-drip agent, which may be pure PTFE or PTFE coated with styrene acrylonitrile copolymer, except It plays a role in anti-drip, and can also significantly reduce the friction coefficient of the material surface, improve the anti-wear performance of the material itself, and at the same time play the role of internal lubrication and demoulding.
  • PTFE polytetrafluoroethylene
  • the component F lubricant of the invention is a graft modified polymer wax, such as graft modified polyethylene wax, graft modified polypropylene wax, graft modified ethylene-vinyl acetate copolymer wax, preferably Maleic anhydride modified polyethylene wax, which is easier to blend and bond with other materials.
  • graft modified polymer wax such as graft modified polyethylene wax, graft modified polypropylene wax, graft modified ethylene-vinyl acetate copolymer wax, preferably Maleic anhydride modified polyethylene wax, which is easier to blend and bond with other materials.
  • the component G pigments described in the present invention are conventionally commercially available pigments for color development.
  • the technical measure adopted by the present invention is to provide an inclusion
  • the preparation method of the antistatic molding composition of the conductive glass fiber comprises the steps of: modifying the polycarbonate resin or the polyester carbonate resin (A), the conductive glass fiber (B), and the anti-shock according to the above weight percentage ratio
  • the agent (C), the flame retardant (D), the anti-drip agent (E), the lubricant (F) and the pigment (G) are mixed by a high-speed mixer, and then subjected to a twin-screw or single-screw extruder.
  • the above preparation method of the antistatic molding composition comprising the conductive glass fiber further comprises the following pretreatment steps:
  • the first step ultrasonically treating the glass fiber in acetone or absolute ethanol or dichloromethane twice, then ultrasonically treating it twice in deionized water, and finally placing it in a hot air drying oven until it is dry;
  • the second step optionally immersing the above-mentioned washed glass fiber into the nano silver glue solution, and after the surface thereof is sufficiently covered by the nano silver glue, it is dried by hot air at 70 to 90 ° C to obtain a surface-plated glass. fiber;
  • the third step dissolving the crystal of tin tetrachloride in absolute ethanol for 15 to 30 minutes, and magnetically stirring to 80 to 85 ° C for 2 to 3 hours until the colorless transparent solution, and then placed in a constant temperature water bath at 30 ° C In the medium aging for 30 to 45 minutes, a stable pure tin dioxide sol is obtained; the cerium trichloride is dissolved in the tin dioxide sol solution according to the mass doping ratio of 5 to 20%, and then refluxed at 80 to 85 ° C. ⁇ 3h, finally placed in a 30 ° C constant temperature water bath for 12h, to obtain an antimony doped tin dioxide sol;
  • the fourth step immersing the first-time washed glass fiber or the second-step silver-plated glass fiber into the sol obtained in the third step, and then uniformly and smoothly pulling out;
  • Step 5 Put the glass fiber impregnated in the fourth step into a drying oven at 80-85 ° C for 30-60 min, and finally put it into a muffle furnace at 450 ° C for 2 h to obtain a conductive glass fiber. Finished product.
  • the beneficial effects of the present invention over the prior art are that the present invention employs conductive glass fibers in place of conventional permanent antistatic agents or carbon fibers, wherein the conductive glass fibers are preferably provided by ruthenium-doped tin oxide conductive sol on the outer surface of the glass fibers.
  • the composition of the composite material is superior to the conductive carbon fiber in the case of the tensile strength, and is easy to color; the antistatic property can be achieved with respect to the PC permanent antistatic agent MH2030.
  • Requires and in the case of close surface resistivity and vertical burning level, it has better tensile strength, bending performance, and better appearance of the product, easy coloring, suitable for environmental conditions of different humidity; Exquisite research, process science, convenient production, low cost, long service life and wide applicability, which is conducive to mass industrial production.
  • the raw materials used in the present invention are commercially available from the following companies:
  • Tin tetrachloride crystal Guangzhou Suyu Chemical Co., Ltd.;
  • Antimony trichloride BEHRINGER TECHNOLOGY CO., LTD.;
  • Component A A1 polycarbonate (referred to as PC), produced by Korea Lotte Chemical Co., Ltd., grade 1100;
  • A2 polyester carbonate (referred to as PEC), produced by Wuhan Hezhong Biochemical Manufacturing Co., Ltd.;
  • Component C epoxy functionalized acrylic core-shell copolymer, manufactured by Dow, under the designation EXL2620;
  • Component D oligomeric bisphenol A bis(diphenyl phosphate) (abbreviated as BDP), produced by Japan Big Eight Company, grade CR741;
  • Component E Polytetrafluoroethylene (PTFE), produced by DuPont, USA, under the designation A3800;
  • Component F maleic anhydride modified polyethylene wax, lubricant, produced by Mitsui, Japan, grade 1105A;
  • Component G red pigment: aminoketone toner, produced by Bayer, USA, grade EG red;
  • Conductive carbon fiber produced by Dongguan Carbon Cable Composite Materials Co., Ltd.;
  • PC permanent antistatic agent MH2030 Shenzhen Jiejiayou Plastic Co., Ltd.
  • the glass fiber was ultrasonically treated twice in dichloromethane, then ultrasonically treated twice in deionized water, and finally placed in a hot air drying oven until dry; then the washed glass fiber was immersed in the nano silver glue solution, After the surface thereof is sufficiently covered with nano silver paste, it is dried by hot air at 70 to 90 ° C to obtain a glass fiber coated with silver on the surface.
  • the above-mentioned washed glass fiber is directly immersed in the cerium-doped tin dioxide sol, and then uniformly and smoothly pulled out vertically; finally, the impregnated glass fiber is placed in a drying oven at 80-85 ° C for 30 min, and finally put The conductive glass fiber finished component B1 was obtained by entering the muffle furnace at a temperature of 450 ° C for 2 h.
  • the above-mentioned surface-plated glass fiber is immersed in an antimony doped tin dioxide sol, and then uniformly and smoothly pulled out vertically; finally, the impregnated glass fiber is placed in a drying oven at 80 to 85 ° C for 30 minutes, and finally It was placed in a muffle furnace at a temperature of 450 ° C for 2 h to obtain a conductive glass fiber finished component B2.
  • the mixer is uniformly mixed, the speed of the high-speed mixer is set to 1400r/min, and the melt extrusion is performed by a twin-screw or single-screw extruder, and the extrusion temperature is 230-300 ° C; and the granules are pelletized by the granulator to produce pellets.
  • a spline having a thickness of 1.6 mm was obtained by injection molding, the temperature of the injection molding machine was set to 270 ° C, and the injection pressure was 70 to 120 bar.
  • the mixer is uniformly mixed, the speed of the high-speed mixer is set to 1400r/min, and the melt extrusion is performed by a twin-screw or single-screw extruder, and the extrusion temperature is 230-300 ° C; and the granules are pelletized by the granulator to produce pellets.
  • a spline having a thickness of 1.6 mm was obtained by injection molding, the temperature of the injection molding machine was set to 270 ° C, and the injection pressure was 70 to 120 bar.
  • the mixer is uniformly mixed, the speed of the high-speed mixer is set to 1400r/min, and the melt extrusion is performed by a twin-screw or single-screw extruder, and the extrusion temperature is 230-300 ° C; and the granules are pelletized by the granulator to produce pellets.
  • a spline having a thickness of 1.6 mm was obtained by injection molding, the temperature of the injection molding machine was set to 270 ° C, and the injection pressure was 70 to 120 bar.
  • the mixer is uniformly mixed, the speed of the high-speed mixer is set to 1400r/min, and the melt extrusion is performed by a twin-screw or single-screw extruder, and the extrusion temperature is 230-300 ° C; and the granules are pelletized by the granulator to produce pellets.
  • a spline having a thickness of 1.6 mm was obtained by injection molding, the temperature of the injection molding machine was set to 270 ° C, and the injection pressure was 70 to 120 bar.
  • the extrusion temperature is 230-300 ° C; and then pelletized by a granulator, the resulting pellets are Drying in an oven at 80 ° C for 4 hours, and then by injection molding to obtain a spline having a thickness of 1.6 mm, the temperature of the injection molding machine was set to 270 ° C, and the injection pressure was 70 to 120 bar.
  • component A1 2.0kg of silver-plated glass fiber, 0.2kg of component C, 1.05kg of component D, 0.3kg of component E, 0.02kg of component F, 0.03kg of red pigment
  • the components are uniformly mixed by a high-speed mixer, the speed of the high-speed mixer is set to 1400r/min, and the melt extrusion is performed by a twin-screw or single-screw extruder, and the extrusion temperature is 230-300 ° C; and then pelletized by a granulator to generate The pellets were dried in an oven at 80 ° C for 4 hours, and then injection molded to obtain a spline having a thickness of 1.6 mm.
  • the temperature of the injection molding machine was set to 270 ° C, and the injection pressure was 70 to 120 bar.
  • Example 1 The test results in the table show that, by using Example 1, Example 2 and Comparative Example 1, it can be seen that the conductive glass fiber is used instead of the conventional conductive carbon fiber, and the Charpy unnotched impact strength (ie, toughness) is equivalent under the tensile strength. It is obviously superior to conductive carbon fiber and easy to color; it can be seen from Example 1, Example 2 and Comparative Example 2 that the permanent antistatic agent MH2030 can be replaced by conductive glass fiber, which can achieve antistatic performance requirements and surface resistance. When the rate and vertical burning level are close, there is better tensile strength, bending performance, Charpy unnotched impact strength, and better appearance of the product, which is easy to color.
  • the rate and vertical burning level are close, there is better tensile strength, bending performance, Charpy unnotched impact strength, and better appearance of the product, which is easy to color.
  • Example 4 Example 5 and Comparative Example 3 that a guide for providing a ruthenium-doped tin oxide conductive sol gel coating layer on the outer surface of the glass fiber is used.
  • the electric glass fiber replaces the conductive glass fiber with the nano silver coating layer on the surface, which can obviously overcome the defect that the nano silver coating layer is easily peeled off, and also has the tensile strength and the flexural modulus.

Abstract

The present invention discloses an antistatic molding composition comprising conductive fiberglass. The composition comprises, by weight percentage, the following: 35-75% of a resin, 20-55% of conductive fiberglass, 2-30% of an impact modifier, 0.5-30% of a flame retardant, 0.2-3% of an anti-drip agent, 0.05-1% of a lubricant, and 0.05-1% of a pigment, wherein the resin is a polycarbonate resin or a polyestercarbonate resin, and a component B may be fiberglass having a conductive sol-gel antimony-doped tin oxide coating layer on an outer surface thereof. The present invention also discloses a method of preparing the antistatic molding composition comprising conductive fiberglass. The antistatic molding composition prepared by the present invention can achieve a permanent antistatic effect, and has the following benefits: easy to be colored, having an aesthetically-pleasing appearance, employing well-chosen materials, having a scientific production process, easy to prepare, having a low cost, long service life, and wide applicability, and suitable for large-scale industrial production.

Description

一种包含导电玻璃纤维的抗静电模塑组合物及其制备方法Antistatic molding composition containing conductive glass fiber and preparation method thereof 技术领域Technical field
本发明属于高分子材料领域，具体涉及一种包含导电玻璃纤维的抗静电模塑组合物及其制备方法。The invention belongs to the field of polymer materials, and in particular relates to an antistatic molding composition comprising conductive glass fibers and a preparation method thereof.
背景技术Background technique
随着科技的发展和人们对家居环境舒适度越发关注，高端智能小家电及智能家居***越来越普及。新兴的小家电，如智能扫地机器人，无线吸尘器等，对外壳类材料除了传统的阻燃和基本机械性能的要求外，因为静电所导致的材料破坏和制程不良等问题增多，同时要求材料具有优异的导电(抗静电)性或防电性。With the development of technology and people's attention to the comfort of the home environment, high-end smart small appliances and smart home systems are becoming more and more popular. Emerging small household appliances, such as smart sweeping robots, wireless vacuum cleaners, etc., in addition to the traditional flame retardant and basic mechanical properties of the shell materials, due to the problem of material damage and poor process caused by static electricity, and the demand for materials is excellent. Conductive (antistatic) or electrical resistance.
传统的永久抗静电材料，一般使用永久抗静电剂或者碳纤维达到永久抗静电的效果。永久抗静电剂，如法国阿科玛公司的MH2030是一种具有特殊的聚醚链段基于聚酰胺基础上合成的助剂，一般这类抗静电剂对环境湿度比较敏感，即湿度大抗静电效果好，反之亦反；而且这类抗静电剂由于其自身的特性不易着色，很难做出鲜艳的颜色，或者注塑过程中易有熔接痕的注塑缺陷影响外观体验。使用碳纤维达到永久抗静电效果的材料，因碳纤维颜色限制，做出的产品外观是黑色的，无法实现彩色的效果。因此有必要开发一种能够达到永久抗静电的效果且易着色，同时能够满足产品各方面要求的改性的抗静电模塑组合物。Traditional permanent antistatic materials generally use permanent antistatic agents or carbon fibers to achieve a permanent antistatic effect. Permanent antistatic agents, such as MH2030 from Arkema, France, are special auxiliaries based on polyamide based on polyether segments. Generally, such antistatic agents are sensitive to environmental humidity, ie, high humidity and antistatic The effect is good, and vice versa; and such antistatic agents are not easy to color due to their own characteristics, it is difficult to make bright colors, or injection molding defects which are prone to weld lines during the injection molding process affect the appearance experience. A material that uses carbon fiber to achieve a permanent antistatic effect, because of the carbon fiber color limitation, the appearance of the product is black, and the color effect cannot be achieved. Therefore, it is necessary to develop a modified antistatic molding composition capable of achieving a permanent antistatic effect and being easily colored while satisfying various requirements of the product.
发明内容Summary of the invention
本发明针对现有技术中存在的不足，提供了一种包含导电玻璃纤 维的抗静电模塑组合物及其制备方法，以解决现有技术中存在的问题。The present invention is directed to the deficiencies in the prior art, and provides a conductive glass fiber. Dimensional antistatic molding compositions and methods for their preparation to solve the problems in the prior art.
本发明可以通过以下技术方案来实现：本发明提供了一种包含导电玻璃纤维的抗静电模塑组合物，以重量百分比计，该组合物包含：35～75％树脂(A)、20～55％导电玻璃纤维(B)、2～30％抗冲改性剂(C)、0.5～30％阻燃剂(D)、0.2～3％抗滴落剂(E),0.05～1％润滑剂(F)和0.05～1％颜料(G)，其中所述树脂为聚碳酸酯树脂或聚酯碳酸酯树脂。The present invention can be achieved by the following technical solutions: The present invention provides an antistatic molding composition comprising conductive glass fibers, the composition comprising: 35 to 75% resin (A), 20 to 55 by weight percent % conductive glass fiber (B), 2 ~ 30% impact modifier (C), 0.5 ~ 30% flame retardant (D), 0.2 ~ 3% anti-drip agent (E), 0.05 ~ 1% lubricant (F) and 0.05 to 1% of the pigment (G), wherein the resin is a polycarbonate resin or a polyester carbonate resin.
本发明的组合物还可以进一步包括任选一种或多种添加剂，如0.1～2％抗氧剂、热稳定剂、光稳定剂、颜料、脱模剂、流动促进剂等。The composition of the present invention may further comprise optionally one or more additives such as 0.1 to 2% of an antioxidant, a heat stabilizer, a light stabilizer, a pigment, a mold release agent, a flow promoter, and the like.
本发明所述的组分A，可以是单一粘度的聚碳酸酯或聚酯碳酸酯，或是不同粘度的聚碳酸酯或聚酯碳酸酯，其可通过酯交换、界面聚合、溶液聚合、本体聚合等方法合成；所述的粘度与组分A分子量、溶液中浓度和温度有关，其中单一粘度或不同粘度的聚碳酸酯或聚酯碳酸酯的平均分子量选自45000～90000。The component A according to the present invention may be a single viscosity polycarbonate or polyester carbonate, or a polycarbonate or polyester carbonate of different viscosity, which can be transesterified, interfacially polymerized, solution polymerized, and bulk. Synthesis by polymerization or the like; the viscosity is related to the molecular weight of the component A, the concentration in the solution, and the temperature, wherein the average molecular weight of the polycarbonate or the polyester carbonate of a single viscosity or a different viscosity is selected from 45,000 to 90,000.
本发明所述的组分B导电玻璃纤维是：先将该导电玻璃纤维的玻璃纤维基底经过前处理后使其具有很好的镀层附着力，然后在玻璃纤维的外表面上设有锑掺杂氧化锡导电溶胶凝胶涂覆层；优选当涂覆层中锑质量含量为5～20％，涂覆层厚度为2～5um时，锑掺杂氧化锡涂覆层能均匀分布在玻璃纤维表面上，使该导电玻璃纤维具有优良的导电性、透明性、耐高温、抗氧化性、抗辐射性，且不受气候环境和使用环境的限制，更持久耐用；更优选在玻璃纤维和锑掺杂氧化锡导电溶胶凝胶涂覆层之间设有纳米银涂覆层，该纳米银涂覆层厚度为2～7um；设置有纳米银涂覆层目的是为了使导电效果更强，并且在纳米 银涂覆层的基础上再设置一层锑掺杂氧化锡导电溶胶凝胶涂覆层是为了防止纳米银涂覆层的脱落。The component B conductive glass fiber of the invention is: the glass fiber substrate of the conductive glass fiber is pretreated to have good coating adhesion, and then the ruthenium doping is provided on the outer surface of the glass fiber. Tin oxide conductive sol gel coating layer; preferably, when the coating layer has a cerium mass content of 5 to 20% and the coating layer has a thickness of 2 to 5 um, the cerium-doped tin oxide coating layer can be uniformly distributed on the surface of the glass fiber The conductive glass fiber has excellent electrical conductivity, transparency, high temperature resistance, oxidation resistance, radiation resistance, and is not limited by the climatic environment and the use environment, and is more durable; more preferably, it is blended in glass fiber and bismuth. a nano silver coating layer is disposed between the tin oxide conductive sol gel coating layer, the nano silver coating layer has a thickness of 2-7 um; and the nano silver coating layer is disposed for the purpose of making the conductive effect stronger, and Nano A layer of antimony-doped tin oxide conductive sol gel coating layer is further provided on the basis of the silver coating layer in order to prevent the nano silver coating layer from falling off.
本发明所述的组分C抗冲改性剂可以是具有核壳结构的共聚物，它是具有弹性体的核和至少一种热塑性的壳组成的细颗粒形式，颗粒的尺寸一般为120～550nm；上述的核壳共聚物的核，可以是：异戊二烯、丁二烯、丙烯酸烷基酯、甲基丙烯酸烷基酯均聚物、硅氧烷橡胶弹性体等；上述的核壳共聚物的壳是苯乙类烯、烷基苯乙烯、丙烯酸烷基酯、甲基丙烯酸烷基酯的一种或两种以上化合物，或它们与包含乙烯基的脂肪族或芳香族乙烯类化合物的共聚物，如苯乙烯、丙烯腈、醋酸乙烯等；该核壳结构共聚物相对其他抗冲改性剂具有更高的抗冲击性能、热分解温度和更好的耐磨性能。The component C impact modifier of the present invention may be a copolymer having a core-shell structure, which is a fine particle form composed of an elastomer core and at least one thermoplastic shell, and the particle size is generally 120 ～. 550 nm; the core of the above core-shell copolymer may be: isoprene, butadiene, alkyl acrylate, alkyl methacrylate homopolymer, silicone rubber elastomer, etc.; The shell of the copolymer is one or two or more compounds of styrene olefin, alkyl styrene, alkyl acrylate, alkyl methacrylate, or an aliphatic or aromatic vinyl compound containing a vinyl group. Copolymers such as styrene, acrylonitrile, vinyl acetate, etc.; the core-shell copolymers have higher impact resistance, thermal decomposition temperature and better wear resistance than other impact modifiers.
本发明所述的组分D结构式中至少包含P＝O双键，如磷酸酯类阻燃剂，具体如苯二酚双磷酸酯、低聚双酚A双(二苯基磷酸酯)、磷酸三丁酯或磷酸三苯酯等，具有阻燃效果持久，与其它材料相容性好，耐水、耐热以及耐迁移等特点。The structural formula D of the present invention contains at least a P=O double bond, such as a phosphate flame retardant, such as benzenediol diphosphate, oligobisphenol A bis(diphenyl phosphate), phosphoric acid. Tributyl ester or triphenyl phosphate has long-lasting flame retardant effect, good compatibility with other materials, water resistance, heat resistance and migration resistance.
本发明所述的组分E抗滴落剂为聚四氟乙烯类(简称PTFE)抗滴落剂，其中可以是纯的PTFE，也可以是包覆苯乙烯丙烯腈共聚物的PTFE，其除了起到抗滴落的作用，还能够明显降低材料表面的摩擦系数，提高材料本身的抗磨损性能，同时能起到内润滑以及脱模的作用。The component E anti-drip agent of the present invention is a polytetrafluoroethylene (PTFE) anti-drip agent, which may be pure PTFE or PTFE coated with styrene acrylonitrile copolymer, except It plays a role in anti-drip, and can also significantly reduce the friction coefficient of the material surface, improve the anti-wear performance of the material itself, and at the same time play the role of internal lubrication and demoulding.
本发明所述的组分F润滑剂为接枝改性高分子蜡，如接枝改性聚乙烯蜡、接枝改性聚丙烯蜡、接枝改性乙烯-乙酸乙烯酯共聚物蜡，优选马来酸酐改性聚乙烯蜡，其更容易与其它材料进行共混和粘接。The component F lubricant of the invention is a graft modified polymer wax, such as graft modified polyethylene wax, graft modified polypropylene wax, graft modified ethylene-vinyl acetate copolymer wax, preferably Maleic anhydride modified polyethylene wax, which is easier to blend and bond with other materials.
本发明所述的组分G颜料就是常规市售用于显色的颜料。The component G pigments described in the present invention are conventionally commercially available pigments for color development.
为实现上述目的，本发明所采取的技术措施是：提供了一种包含 导电玻璃纤维的抗静电模塑组合物的制备方法，包括如下步骤：按照上述重量百分比配比，将聚碳酸酯树脂或聚酯碳酸酯树脂(A)、导电玻璃纤维(B)、抗冲改性剂(C)、阻燃剂(D)、抗滴落剂(E)、润滑剂(F)和颜料(G)经过高速混合机混匀后，再经双螺杆或单螺杆挤出机进行熔融挤出；再经造粒机切粒，生成的粒料在80℃烘箱中干燥4小时，然后通过注塑成型得到；其中高速混合机转速为800～1500r/min，挤出温度为230～300℃。In order to achieve the above object, the technical measure adopted by the present invention is to provide an inclusion The preparation method of the antistatic molding composition of the conductive glass fiber comprises the steps of: modifying the polycarbonate resin or the polyester carbonate resin (A), the conductive glass fiber (B), and the anti-shock according to the above weight percentage ratio The agent (C), the flame retardant (D), the anti-drip agent (E), the lubricant (F) and the pigment (G) are mixed by a high-speed mixer, and then subjected to a twin-screw or single-screw extruder. Melt extrusion; granulation by pelletizer, the resulting pellets are dried in an oven at 80 ° C for 4 hours, and then obtained by injection molding; wherein the high speed mixer rotates at 800-1500 r/min and the extrusion temperature is 230-300. °C.
上述包含导电玻璃纤维的抗静电模塑组合物的制备方法，进一步包括如下预处理步骤：The above preparation method of the antistatic molding composition comprising the conductive glass fiber further comprises the following pretreatment steps:
第一步：将玻璃纤维在丙酮或无水乙醇或二氯甲烷中超声波处理2次，然后放入去离子水中超声波处理2次，最后放入热风干燥箱中直至干燥；The first step: ultrasonically treating the glass fiber in acetone or absolute ethanol or dichloromethane twice, then ultrasonically treating it twice in deionized water, and finally placing it in a hot air drying oven until it is dry;
第二步：可选地将上述清洗过的玻璃纤维浸入到纳米银胶溶液中，待其表面被所述纳米银胶充分覆盖后，用70～90℃热风吹干，得到表面镀银的玻璃纤维；The second step: optionally immersing the above-mentioned washed glass fiber into the nano silver glue solution, and after the surface thereof is sufficiently covered by the nano silver glue, it is dried by hot air at 70 to 90 ° C to obtain a surface-plated glass. fiber;
第三步：将四氯化锡晶体溶解在无水乙醇中超声震荡15～30min，并通过加热到80～85℃磁力搅拌2～3h,直至无色透明溶液，然后放在30℃恒温水浴锅中陈化30～45min，得到稳定的纯二氧化锡溶胶；按照5～20％的质量掺杂比称取三氯化锑溶解在二氧化锡溶胶溶液中，再在80～85℃下回流2～3h，最后放入30℃恒温水浴锅中12h，得到锑掺杂的二氧化锡溶胶；The third step: dissolving the crystal of tin tetrachloride in absolute ethanol for 15 to 30 minutes, and magnetically stirring to 80 to 85 ° C for 2 to 3 hours until the colorless transparent solution, and then placed in a constant temperature water bath at 30 ° C In the medium aging for 30 to 45 minutes, a stable pure tin dioxide sol is obtained; the cerium trichloride is dissolved in the tin dioxide sol solution according to the mass doping ratio of 5 to 20%, and then refluxed at 80 to 85 ° C. ~3h, finally placed in a 30 ° C constant temperature water bath for 12h, to obtain an antimony doped tin dioxide sol;
第四步：将第一步清洗过的玻璃纤维或第二步表面镀银的玻璃纤维浸入到第三步得到的溶胶中，然后均匀平稳垂直提拉出来；The fourth step: immersing the first-time washed glass fiber or the second-step silver-plated glass fiber into the sol obtained in the third step, and then uniformly and smoothly pulling out;
第五步：将第四步浸渍过的玻璃纤维放入80～85℃的干燥箱中30～60min，最后放入马弗炉中在450℃温度下2h，得到导电玻璃纤 维成品。Step 5: Put the glass fiber impregnated in the fourth step into a drying oven at 80-85 ° C for 30-60 min, and finally put it into a muffle furnace at 450 ° C for 2 h to obtain a conductive glass fiber. Finished product.
本发明相对于现有技术的有益效果是本发明采用导电玻璃纤维代替传统的永久抗静电剂或者碳纤维，其中导电玻璃纤维优选通过在玻璃纤维的外表面上设有锑掺杂氧化锡导电溶胶凝胶涂覆层，这类组合物材料相对传统的导电碳纤维，在拉伸强度相当的情况下，韧性明显优于导电碳纤维，且易于着色；相对PC永久抗静电剂MH2030，能够达到抗静电的性能要求，而且在表面电阻率及垂直燃烧等级接近的情况下，有更好的拉伸强度、弯曲性能，以及使产品具有更好的外观性状，容易着色，适用于不同湿度的环境条件；选料考究，工艺科学，制作方便，成本低，使用寿命长，适用性广，有利于大批量工业化生产。The beneficial effects of the present invention over the prior art are that the present invention employs conductive glass fibers in place of conventional permanent antistatic agents or carbon fibers, wherein the conductive glass fibers are preferably provided by ruthenium-doped tin oxide conductive sol on the outer surface of the glass fibers. Compared with the traditional conductive carbon fiber, the composition of the composite material is superior to the conductive carbon fiber in the case of the tensile strength, and is easy to color; the antistatic property can be achieved with respect to the PC permanent antistatic agent MH2030. Requires, and in the case of close surface resistivity and vertical burning level, it has better tensile strength, bending performance, and better appearance of the product, easy coloring, suitable for environmental conditions of different humidity; Exquisite research, process science, convenient production, low cost, long service life and wide applicability, which is conducive to mass industrial production.
具体实施方式detailed description
下面结合具体实施方式，进一步阐明本发明。The invention will be further elucidated in the following in conjunction with specific embodiments.
本发明所用的原材料从以下公司购得：The raw materials used in the present invention are commercially available from the following companies:
100mg/L Ag溶液：深圳市时得佳科技有限公司；100mg/L Ag solution: Shenzhen Shidejia Technology Co., Ltd.;
2％柠檬酸三钠溶液：西亚试剂公司；2% trisodium citrate solution: West Asia Reagent Company;
四氯化锡晶体：广州苏喏化工有限公司；Tin tetrachloride crystal: Guangzhou Suyu Chemical Co., Ltd.;
三氯化锑：百灵威科技有限公司；Antimony trichloride: BEHRINGER TECHNOLOGY CO., LTD.;
组分A：A1聚碳酸酯(简称PC)，韩国乐天化学公司生产，牌号为1100；Component A: A1 polycarbonate (referred to as PC), produced by Korea Lotte Chemical Co., Ltd., grade 1100;
A2聚酯碳酸酯(简称PEC)，武汉合中生化制造有限公司生产；A2 polyester carbonate (referred to as PEC), produced by Wuhan Hezhong Biochemical Manufacturing Co., Ltd.;
玻璃纤维，江苏双山集团生产； Glass fiber, produced by Jiangsu Shuangshan Group;
组分C：环氧官能化的丙烯酸核-壳型共聚物，Dow公司生产，牌号EXL2620；Component C: epoxy functionalized acrylic core-shell copolymer, manufactured by Dow, under the designation EXL2620;
组分D：低聚双酚A双(二苯基磷酸酯)(简称BDP)，日本大八公司生产，牌号为CR741；Component D: oligomeric bisphenol A bis(diphenyl phosphate) (abbreviated as BDP), produced by Japan Big Eight Company, grade CR741;
组分E：聚四氟乙烯(简称PTFE)，美国杜邦公司生产，牌号为
Figure PCTCN2016108007-appb-000001
A3800；Component E: Polytetrafluoroethylene (PTFE), produced by DuPont, USA, under the designation
Figure PCTCN2016108007-appb-000001
A3800;
组分F：马来酸酐改性聚乙烯蜡，润滑剂，日本三井公司生产，牌号为1105A；Component F: maleic anhydride modified polyethylene wax, lubricant, produced by Mitsui, Japan, grade 1105A;
组分G：红色颜料:氨基酮色粉，美国拜耳公司生产，牌号为EG红；Component G: red pigment: aminoketone toner, produced by Bayer, USA, grade EG red;
导电碳纤维：东莞市碳索复合材料有限公司生产；Conductive carbon fiber: produced by Dongguan Carbon Cable Composite Materials Co., Ltd.;
PC永久抗静电剂MH2030:深圳市杰嘉友塑胶有限公司。PC permanent antistatic agent MH2030: Shenzhen Jiejiayou Plastic Co., Ltd.
准备例1：Preparation Example 1:
将100ml 100mg/L Ag溶液于小烧杯中，加入100ml 2％柠檬酸三钠溶液，置于254nm紫外光下照射60min，得到黄褐色高分散性纳米银胶溶液。100 ml of 100 mg/L Ag solution was placed in a small beaker, 100 ml of 2% trisodium citrate solution was added, and irradiated under ultraviolet light of 254 nm for 60 min to obtain a yellow-brown highly dispersible nano silver gum solution.
将玻璃纤维在二氯甲烷中超声波处理2次，然后放入去离子水中超声波处理2次，最后放入热风干燥箱中直至干燥；然后将清洗过的玻璃纤维浸入到纳米银胶溶液中，待其表面被纳米银胶充分覆盖后，用70～90℃热风吹干，得到表面镀银的玻璃纤维。The glass fiber was ultrasonically treated twice in dichloromethane, then ultrasonically treated twice in deionized water, and finally placed in a hot air drying oven until dry; then the washed glass fiber was immersed in the nano silver glue solution, After the surface thereof is sufficiently covered with nano silver paste, it is dried by hot air at 70 to 90 ° C to obtain a glass fiber coated with silver on the surface.
将70.1g四氯化锡晶体溶解在200ml无水乙醇中超声震荡20min，并通过加热到80～85℃磁力搅拌2.5h,直至无色透明溶液，然 后放在30℃恒温水浴锅中陈化30min，得到稳定的纯二氧化锡溶胶；按照5％的质量掺杂比称取2.3g三氯化锑溶解在二氧化锡溶胶溶液中，再在80～85℃下回流2.5h，最后放入30℃恒温水浴锅中12h，得到锑掺杂的二氧化锡溶胶。70.1 g of tin tetrachloride crystals were dissolved in 200 ml of absolute ethanol, ultrasonically shaken for 20 min, and magnetically stirred by heating to 80-85 ° C for 2.5 h until a colorless transparent solution. After being aged in a constant temperature water bath at 30 ° C for 30 min, a stable pure tin dioxide sol is obtained; 2.3 g of antimony trichloride is dissolved in the tin dioxide sol solution according to a mass doping ratio of 5%, and then at 80 It was refluxed at ~85 ° C for 2.5 h, and finally placed in a constant temperature water bath at 30 ° C for 12 h to obtain an antimony doped tin dioxide sol.
将上述清洗过的玻璃纤维直接浸入到锑掺杂的二氧化锡溶胶中，然后均匀平稳垂直提拉出来；最后将上述浸渍过的玻璃纤维放入80～85℃的干燥箱中30min，最后放入马弗炉中在450℃温度下2h，得到导电玻璃纤维成品组分B1。The above-mentioned washed glass fiber is directly immersed in the cerium-doped tin dioxide sol, and then uniformly and smoothly pulled out vertically; finally, the impregnated glass fiber is placed in a drying oven at 80-85 ° C for 30 min, and finally put The conductive glass fiber finished component B1 was obtained by entering the muffle furnace at a temperature of 450 ° C for 2 h.
或者将上述表面镀银的玻璃纤维浸入到锑掺杂的二氧化锡溶胶中，然后均匀平稳垂直提拉出来；最后将上述浸渍过的玻璃纤维放入80～85℃的干燥箱中30min，最后放入马弗炉中在450℃温度下2h，得到导电玻璃纤维成品组分B2。Alternatively, the above-mentioned surface-plated glass fiber is immersed in an antimony doped tin dioxide sol, and then uniformly and smoothly pulled out vertically; finally, the impregnated glass fiber is placed in a drying oven at 80 to 85 ° C for 30 minutes, and finally It was placed in a muffle furnace at a temperature of 450 ° C for 2 h to obtain a conductive glass fiber finished component B2.
实施例1：Example 1:
分别称取4.2kg组分A1，4.0kg组分B1，0.5kg组分C，1.25kg组分D，0.02kg组分E，0.02kg组分F，0.01kg红色颜料，将以上各成分经过高速混合机混合均匀，高速混合机转速设置为1400r/min，经双螺杆或单螺杆挤出机进行熔融挤出，挤出温度为230～300℃；再经造粒机切粒，生成的粒料在80℃烘箱中干燥4小时，然后通过注塑成型得到厚度为1.6mm的样条，注塑机温度设置为270℃，注塑压力为70～120bar。Weigh 4.2kg component A1, 4.0kg component B1, 0.5kg component C, 1.25kg component D, 0.02kg component E, 0.02kg component F, 0.01kg red pigment, and pass the above components through high speed. The mixer is uniformly mixed, the speed of the high-speed mixer is set to 1400r/min, and the melt extrusion is performed by a twin-screw or single-screw extruder, and the extrusion temperature is 230-300 ° C; and the granules are pelletized by the granulator to produce pellets. After drying in an oven at 80 ° C for 4 hours, a spline having a thickness of 1.6 mm was obtained by injection molding, the temperature of the injection molding machine was set to 270 ° C, and the injection pressure was 70 to 120 bar.
实施例2：Example 2:
分别称取4.2kg组分A2，4.0kg组分B1，0.5kg组分C，1.25kg 组分D，0.02kg组分E，0.02kg组分F，0.01kg红色颜料，将以上各成分经过高速混合机混合均匀，高速混合机转速设置为1400r/min，经双螺杆或单螺杆挤出机进行熔融挤出，挤出温度为230～300℃；再经造粒机切粒，生成的粒料在80℃烘箱中干燥4小时，然后通过注塑成型得到厚度为1.6mm的样条，注塑机温度设置为270℃，注塑压力为70～120bar。Weigh 4.2kg component A2, 4.0kg component B1, 0.5kg component C, 1.25kg Component D, 0.02kg component E, 0.02kg component F, 0.01kg red pigment, the above components are uniformly mixed by a high-speed mixer, the high-speed mixer speed is set to 1400r/min, and the twin-screw or single-screw extrusion The machine is melt extruded, and the extrusion temperature is 230-300 ° C; the pellet is pelletized by a granulator, and the resulting pellets are dried in an oven at 80 ° C for 4 hours, and then splined to obtain a spline having a thickness of 1.6 mm, and injection molded. The machine temperature was set to 270 ° C and the injection pressure was 70 to 120 bar.
实施例3：Example 3:
分别称取3.5kg组分A1，5.5kg组分B1，0.2kg组分C，0.7kg组分D，0.05kg组分E，0.04kg组分F，0.01kg红色颜料，将以上各成分经过高速混合机混合均匀，高速混合机转速设置为1400r/min，经双螺杆或单螺杆挤出机进行熔融挤出，挤出温度为230～300℃；再经造粒机切粒，生成的粒料在80℃烘箱中干燥4小时，然后通过注塑成型得到厚度为1.6mm的样条，注塑机温度设置为270℃，注塑压力为70～120bar。Weigh 3.5kg component A1, 5.5kg component B1, 0.2kg component C, 0.7kg component D, 0.05kg component E, 0.04kg component F, 0.01kg red pigment, and pass the above components through high speed. The mixer is uniformly mixed, the speed of the high-speed mixer is set to 1400r/min, and the melt extrusion is performed by a twin-screw or single-screw extruder, and the extrusion temperature is 230-300 ° C; and the granules are pelletized by the granulator to produce pellets. After drying in an oven at 80 ° C for 4 hours, a spline having a thickness of 1.6 mm was obtained by injection molding, the temperature of the injection molding machine was set to 270 ° C, and the injection pressure was 70 to 120 bar.
实施例4：Example 4:
分别称取6.4kg组分A1，2.0kg组分B1，0.2kg组分C，1.05kg组分D，0.3kg组分E，0.02kg组分F，0.03kg红色颜料，将以上各成分经过高速混合机混合均匀，高速混合机转速设置为1400r/min，经双螺杆或单螺杆挤出机进行熔融挤出，挤出温度为230～300℃；再经造粒机切粒，生成的粒料在80℃烘箱中干燥4小时，然后通过注塑成型得到厚度为1.6mm的样条，注塑机温度设置为270℃，注塑压力为70～120bar。 Weigh 6.4kg component A1, 2.0kg component B1, 0.2kg component C, 1.05kg component D, 0.3kg component E, 0.02kg component F, 0.03kg red pigment, and pass the above components through high speed. The mixer is uniformly mixed, the speed of the high-speed mixer is set to 1400r/min, and the melt extrusion is performed by a twin-screw or single-screw extruder, and the extrusion temperature is 230-300 ° C; and the granules are pelletized by the granulator to produce pellets. After drying in an oven at 80 ° C for 4 hours, a spline having a thickness of 1.6 mm was obtained by injection molding, the temperature of the injection molding machine was set to 270 ° C, and the injection pressure was 70 to 120 bar.
实施例5：Example 5:
分别称取6.4kg组分A1，2.0kg组分B2，0.2kg组分C，1.05kg组分D，0.3kg组分E，0.02kg组分F，0.03kg红色颜料，将以上各成分经过高速混合机混合均匀，高速混合机转速设置为1400r/min，经双螺杆或单螺杆挤出机进行熔融挤出，挤出温度为230～300℃；再经造粒机切粒，生成的粒料在80℃烘箱中干燥4小时，然后通过注塑成型得到厚度为1.6mm的样条，注塑机温度设置为270℃，注塑压力为70～120bar。Weigh 6.4kg component A1, 2.0kg component B2, 0.2kg component C, 1.05kg component D, 0.3kg component E, 0.02kg component F, 0.03kg red pigment, and pass the above components through high speed. The mixer is uniformly mixed, the speed of the high-speed mixer is set to 1400r/min, and the melt extrusion is performed by a twin-screw or single-screw extruder, and the extrusion temperature is 230-300 ° C; and the granules are pelletized by the granulator to produce pellets. After drying in an oven at 80 ° C for 4 hours, a spline having a thickness of 1.6 mm was obtained by injection molding, the temperature of the injection molding machine was set to 270 ° C, and the injection pressure was 70 to 120 bar.
对比例1：Comparative example 1:
分别称取4.2kg组分A1，4.0kg导电碳纤维，0.5kg组分C，1.25kg组分D，0.02kg组分E，0.02kg组分F，0.01kg红色颜料，将以上各成分经过高速混合机混合均匀，高速混合机转速设置为1400r/min，经双螺杆或单螺杆挤出机进行熔融挤出，挤出温度为230～300℃；再经造粒机切粒，生成的粒料在80℃烘箱中干燥4小时，然后通过注塑成型得到厚度为1.6mm的样条，注塑机温度设置为270℃，注塑压力为70～120bar。Weigh 4.2kg component A1, 4.0kg conductive carbon fiber, 0.5kg component C, 1.25kg component D, 0.02kg component E, 0.02kg component F, 0.01kg red pigment, and mix the above components at high speed. The machine is evenly mixed, the high-speed mixer is set to a speed of 1400r/min, and is melt-extruded by a twin-screw or single-screw extruder. The extrusion temperature is 230-300 ° C; and then pelletized by a granulator, the resulting pellets are Drying in an oven at 80 ° C for 4 hours, and then by injection molding to obtain a spline having a thickness of 1.6 mm, the temperature of the injection molding machine was set to 270 ° C, and the injection pressure was 70 to 120 bar.
对比例2：Comparative example 2:
分别称取4.2kg组分A1，4.0kg PC永久抗静电剂MH2030，0.5kg组分C，1.25kg组分D，0.02kg组分E，0.02kg组分F，0.01kg红色颜料，将以上各成分经过高速混合机混合均匀，高速混合机转速设置为1400r/min，经双螺杆或单螺杆挤出机进行熔融挤出，挤出温度为230～300℃；再经造粒机切粒，生成的粒料在80℃烘箱中干燥4小 时，然后通过注塑成型得到厚度为1.6mm的样条，注塑机温度设置为270℃，注塑压力为70～120bar。Weigh 4.2kg component A1, 4.0kg PC permanent antistatic agent MH2030, 0.5kg component C, 1.25kg component D, 0.02kg component E, 0.02kg component F, 0.01kg red pigment, The components are uniformly mixed by a high-speed mixer, the speed of the high-speed mixer is set to 1400r/min, and the melt extrusion is performed by a twin-screw or single-screw extruder, and the extrusion temperature is 230-300 ° C; and then pelletized by a granulator to generate The pellets are dried in an oven at 80 ° C for 4 small Then, a spline having a thickness of 1.6 mm was obtained by injection molding, and the temperature of the injection molding machine was set to 270 ° C, and the injection pressure was 70 to 120 bar.
对比例3：Comparative example 3:
分别称取6.4kg组分A1，2.0kg表面镀银的玻璃纤维，0.2kg组分C，1.05kg组分D，0.3kg组分E，0.02kg组分F，0.03kg红色颜料，将以上各成分经过高速混合机混合均匀，高速混合机转速设置为1400r/min，经双螺杆或单螺杆挤出机进行熔融挤出，挤出温度为230～300℃；再经造粒机切粒，生成的粒料在80℃烘箱中干燥4小时，然后通过注塑成型得到厚度为1.6mm的样条，注塑机温度设置为270℃，注塑压力为70～120bar。Weigh 6.4kg of component A1, 2.0kg of silver-plated glass fiber, 0.2kg of component C, 1.05kg of component D, 0.3kg of component E, 0.02kg of component F, 0.03kg of red pigment, The components are uniformly mixed by a high-speed mixer, the speed of the high-speed mixer is set to 1400r/min, and the melt extrusion is performed by a twin-screw or single-screw extruder, and the extrusion temperature is 230-300 ° C; and then pelletized by a granulator to generate The pellets were dried in an oven at 80 ° C for 4 hours, and then injection molded to obtain a spline having a thickness of 1.6 mm. The temperature of the injection molding machine was set to 270 ° C, and the injection pressure was 70 to 120 bar.
分别观察上述实施例和对比例所得材料的的外观性状及测试相应的物理性能，根据ISO527测试材料的拉伸强度，根据ISO178测试材料的弯曲性能，根据ISO 179测试材料的冲击性能，根据GB/T1410-2006采用三电极法测定材料表面电阻值，并换算成对应的表面电阻率；采用UL94燃烧仪对材料(1.6mm)的阻燃性质进行测定，具体结果见下表1所示。Observe the appearance properties of the materials obtained in the above examples and comparative examples and test the corresponding physical properties. According to the tensile strength of ISO 527 test materials, according to the bending properties of ISO 178 test materials, the impact properties of the test materials according to ISO 179, according to GB/ T1410-2006 used three-electrode method to determine the surface resistance of the material and converted it into the corresponding surface resistivity. The flame retardant properties of the material (1.6mm) were measured by UL94 burner. The specific results are shown in Table 1 below.
表1：实施例和对比例材料性能检测结果Table 1: Performance test results of the examples and comparative materials
Figure PCTCN2016108007-appb-000002
Figure PCTCN2016108007-appb-000002
Figure PCTCN2016108007-appb-000003
Figure PCTCN2016108007-appb-000003
表中测试结果表明：通过实施例1、实施例2和对比例1可以看出，用导电玻璃纤维代替传统的导电碳纤维，在拉伸强度相当的情况下，Charpy无缺口冲击强度(即韧性)明显优于导电碳纤维，且易于着色；通过实施例1、实施例2和对比例2可以看出，用导电玻璃纤维代替PC永久抗静电剂MH2030，能够达到抗静电的性能要求，而且在表面电阻率及垂直燃烧等级接近的情况下，有更好的拉伸强度、弯曲性能、Charpy无缺口冲击强度，以及使产品具有更好的外观性状，容易着色。通过实施例4、实施例5和对比例3可以看出，使用在玻璃纤维的外表面上设有锑掺杂氧化锡导电溶胶凝胶涂覆层的导 电玻璃纤维代替表面设有纳米银涂覆层的导电玻璃纤维，能明显克服纳米银涂覆层容易剥落的缺陷，而且拉伸强度和弯曲模量上也有所提高。The test results in the table show that, by using Example 1, Example 2 and Comparative Example 1, it can be seen that the conductive glass fiber is used instead of the conventional conductive carbon fiber, and the Charpy unnotched impact strength (ie, toughness) is equivalent under the tensile strength. It is obviously superior to conductive carbon fiber and easy to color; it can be seen from Example 1, Example 2 and Comparative Example 2 that the permanent antistatic agent MH2030 can be replaced by conductive glass fiber, which can achieve antistatic performance requirements and surface resistance. When the rate and vertical burning level are close, there is better tensile strength, bending performance, Charpy unnotched impact strength, and better appearance of the product, which is easy to color. It can be seen from Example 4, Example 5 and Comparative Example 3 that a guide for providing a ruthenium-doped tin oxide conductive sol gel coating layer on the outer surface of the glass fiber is used. The electric glass fiber replaces the conductive glass fiber with the nano silver coating layer on the surface, which can obviously overcome the defect that the nano silver coating layer is easily peeled off, and also has the tensile strength and the flexural modulus.
上述实施例仅为本发明的优选技术方案，而不应视为对于本发明的限制，本发明的保护范围应以权利要求记载的技术方案，包括权利要求记载的技术方案中技术特征的等同替换方案为保护范围，即在此范围内的等同替换改进，也在本发明的保护范围之内。 The above-mentioned embodiments are only the preferred technical solutions of the present invention, and should not be construed as limiting the present invention. The scope of the present invention should be construed as the technical solutions described in the claims, including the equivalents of the technical features in the technical solutions recited in the claims. It is also within the scope of the invention to provide a scope of protection, i.e. equivalent replacement improvements within this scope.

Claims (10)

  1. 一种包含导电玻璃纤维的抗静电模塑组合物，其特征在于：以重量百分比计，该组合物包含：35～75％树脂、20～55％导电玻璃纤维、2～30％抗冲改性剂、0.5～30％阻燃剂、0.2～3％抗滴落剂、0.05～1％润滑剂和0.05～1％颜料，其中所述树脂为聚碳酸酯树脂或聚酯碳酸酯树脂。An antistatic molding composition comprising conductive glass fibers, characterized in that, by weight percentage, the composition comprises: 35 to 75% resin, 20 to 55% conductive glass fiber, 2 to 30% impact modification A 0.5 to 30% flame retardant, 0.2 to 3% anti-drip agent, 0.05 to 1% lubricant and 0.05 to 1% pigment, wherein the resin is a polycarbonate resin or a polyester carbonate resin.
  2. 根据权利要求1所述的包含导电玻璃纤维的抗静电模塑组合物，其特征在于：所述的导电玻璃纤维是指在玻璃纤维的外表面上设有锑掺杂氧化锡导电溶胶凝胶涂覆层，该涂覆层中锑质量含量为5～20％，涂覆层厚度为2～5um。The antistatic molding composition comprising conductive glass fibers according to claim 1, wherein the conductive glass fibers are provided with an antimony-doped tin oxide conductive sol gel coating on the outer surface of the glass fibers. The coating layer has a cerium mass content of 5 to 20% and a coating layer thickness of 2 to 5 um.
  3. 根据权利要求2所述的包含导电玻璃纤维的抗静电模塑组合物，其特征在于：所述的导电玻璃纤维还可进一步在玻璃纤维和锑掺杂氧化锡导电溶胶凝胶涂覆层之间设有纳米银涂覆层，该纳米银涂覆层厚度为2～7um。The antistatic molding composition comprising conductive glass fibers according to claim 2, wherein said conductive glass fibers are further further between the glass fibers and the antimony-doped tin oxide conductive sol gel coating layer. A nano silver coating layer is provided, and the nano silver coating layer has a thickness of 2-7 um.
  4. 根据权利要求1所述的包含导电玻璃纤维的抗静电模塑组合物，其特征在于：所述的树脂是单一粘度的聚碳酸酯或聚酯碳酸酯，或是不同粘度的聚碳酸酯或聚酯碳酸酯。The antistatic molding composition comprising conductive glass fibers according to claim 1, wherein the resin is a single viscosity polycarbonate or polyester carbonate, or a polycarbonate or a polymer having a different viscosity. Ester carbonate.
  5. 根据权利要求1所述的包含导电玻璃纤维的抗静电模塑组合物，其特征在于：所述的抗冲改性剂是具有核壳结构的共聚物，它是具有弹性体的核和热塑性的壳组成的细颗粒形式，颗粒的尺寸为120～550nm；上述的核壳共聚物的核是：异戊二烯、丁二烯、丙烯酸烷基酯、甲基丙烯酸烷基酯均聚物、硅氧烷橡胶弹性体；上述的壳是苯乙 烯、烷基苯乙烯、丙烯酸烷基酯、甲基丙烯酸烷基酯中的一种或两种以上化合物，或它们与包含乙烯基的脂肪族或芳香族乙烯类化合物的共聚物。The antistatic molding composition comprising conductive glass fibers according to claim 1, wherein said impact modifier is a core-shell copolymer, which is an elastomer core and thermoplastic. The fine particle form of the shell, the size of the particles is 120-550 nm; the core of the above core-shell copolymer is: isoprene, butadiene, alkyl acrylate, alkyl methacrylate homopolymer, silicon Oxylate rubber elastomer; the above shell is styrene One or two or more compounds of an alkyl group, an alkyl styrene, an alkyl acrylate, an alkyl methacrylate, or a copolymer thereof with an aliphatic or aromatic vinyl compound containing a vinyl group.
  6. 根据权利要求1所述的包含导电玻璃纤维的抗静电模塑组合物，其特征在于：所述的阻燃剂为磷酸酯类阻燃剂。The antistatic molding composition comprising conductive glass fibers according to claim 1, wherein the flame retardant is a phosphate flame retardant.
  7. 根据权利要求6所述的包含导电玻璃纤维的抗静电模塑组合物，其特征在于：所述的磷酸酯类阻燃剂为苯二酚双磷酸酯、低聚双酚A双(二苯基磷酸酯)、磷酸三丁酯或磷酸三苯酯。The antistatic molding composition comprising conductive glass fibers according to claim 6, wherein the phosphate flame retardant is benzenediol diphosphate, oligobisphenol A bis(diphenyl) Phosphate), tributyl phosphate or triphenyl phosphate.
  8. 根据权利要求1所述的包含导电玻璃纤维的抗静电模塑组合物，其特征在于：所述的抗滴落剂为聚四氟乙烯，所述的润滑剂为马来酸酐改性聚乙烯蜡。The antistatic molding composition comprising conductive glass fibers according to claim 1, wherein the anti-drip agent is polytetrafluoroethylene, and the lubricant is maleic anhydride-modified polyethylene wax. .
  9. 一种权利要求1所述的包含导电玻璃纤维的抗静电模塑组合物的制备方法，其特征在于包括如下步骤：按照权利要求1所述的重量百分比配比，将聚碳酸酯树脂或聚酯碳酸酯树脂，与其它物料导电玻璃纤维、抗冲改性剂、阻燃剂、抗滴落剂、润滑剂和颜料经过高速混合机混匀后，经双螺杆或单螺杆挤出机进行熔融挤出，挤出温度为230～300℃；再经造粒机切粒，生成的粒料在80℃烘箱中干燥4小时，然后通过注塑成型得到；其中高速混合机转速为800～1500r/min，挤出温度为230～300℃。A method for producing an antistatic molding composition comprising conductive glass fibers according to claim 1, comprising the steps of: polycarbonate resin or polyester according to the weight percentage ratio according to claim 1. Carbonate resin, mixed with other materials conductive glass fiber, impact modifier, flame retardant, anti-drip agent, lubricant and pigment through high-speed mixer, melt-squeezed through twin-screw or single-screw extruder The extrusion temperature is 230-300 ° C; the pellets are pelletized by a granulator, and the resulting pellets are dried in an oven at 80 ° C for 4 hours, and then obtained by injection molding; wherein the high-speed mixer rotates at 800-1500 r/min. The extrusion temperature is 230 to 300 °C.
  10. 一种权利要求9所述的包含导电玻璃纤维的抗静电模塑组合物的制备方法，其特征在于进一步包括如下预处理步骤：A method of preparing an antistatic molding composition comprising conductive glass fibers according to claim 9, further comprising the following pretreatment steps:
    第一步：将玻璃纤维在丙酮或无水乙醇或二氯甲烷中超声波处理 2次，然后放入去离子水中超声波处理2次，最后放入热风干燥箱中直至干燥；Step 1: Ultrasonic treatment of glass fibers in acetone or absolute ethanol or dichloromethane 2 times, then placed in deionized water for 2 times, and finally placed in a hot air drying oven until dry;
    第二步：可选地将上述清洗过的玻璃纤维浸入到纳米银胶溶液中，待其表面被所述纳米银胶充分覆盖后，用70～90℃热风吹干，得到表面镀银的玻璃纤维；The second step: optionally immersing the above-mentioned washed glass fiber into the nano silver glue solution, and after the surface thereof is sufficiently covered by the nano silver glue, it is dried by hot air at 70 to 90 ° C to obtain a surface-plated glass. fiber;
    第三步：将四氯化锡晶体溶解在无水乙醇中超声震荡15～30min，并通过加热到80～85℃磁力搅拌2～3h,直至无色透明溶液，然后放在30℃恒温水浴锅中陈化3～45min，得到稳定的纯二氧化锡溶胶；按照5～20％的质量掺杂比称取三氯化锑溶解在二氧化锡溶胶溶液中，再在80～85℃下回流2～3h，最后放入30℃恒温水浴锅中12h，得到锑掺杂的二氧化锡溶胶；The third step: dissolving the crystal of tin tetrachloride in absolute ethanol for 15 to 30 minutes, and magnetically stirring to 80 to 85 ° C for 2 to 3 hours until the colorless transparent solution, and then placed in a constant temperature water bath at 30 ° C In the middle aging for 3 to 45 minutes, a stable pure tin dioxide sol is obtained; the cerium trichloride is dissolved in the tin dioxide sol solution according to the mass doping ratio of 5 to 20%, and then refluxed at 80 to 85 ° C. ~3h, finally placed in a 30 ° C constant temperature water bath for 12h, to obtain an antimony doped tin dioxide sol;
    第四步：将第一步清洗过的玻璃纤维或第二步表面镀银的玻璃纤维浸入到第三步得到的溶胶中，然后均匀平稳垂直提拉出来；The fourth step: immersing the first-time washed glass fiber or the second-step silver-plated glass fiber into the sol obtained in the third step, and then uniformly and smoothly pulling out;
    第五步：将第四步浸渍过的玻璃纤维放入80～85℃的干燥箱中30～60min，最后放入马弗炉中在450℃温度下2h，得到导电玻璃纤维成品。 Step 5: The glass fiber impregnated in the fourth step is placed in a drying oven at 80-85 ° C for 30-60 min, and finally placed in a muffle furnace at a temperature of 450 ° C for 2 h to obtain a finished conductive glass fiber.
PCT/CN2016/108007 2016-08-24 2016-11-30 Antistatic molding composition comprising conductive fiberglass, and method of preparing same WO2018036017A1 (en)

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