WO2023005726A1 - Antistatic polyamide composition, preparation method therefor, and use thereof - Google Patents

Antistatic polyamide composition, preparation method therefor, and use thereof Download PDF

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WO2023005726A1
WO2023005726A1 PCT/CN2022/106378 CN2022106378W WO2023005726A1 WO 2023005726 A1 WO2023005726 A1 WO 2023005726A1 CN 2022106378 W CN2022106378 W CN 2022106378W WO 2023005726 A1 WO2023005726 A1 WO 2023005726A1
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Prior art keywords
fiber
polyamide
antistatic
carbon
polyamide composition
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PCT/CN2022/106378
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French (fr)
Chinese (zh)
Inventor
叶少勇
杨硕
陈家达
黄险波
徐显骏
姜苏俊
曹民
龙杰明
麦杰鸿
陈平绪
叶南飚
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金发科技股份有限公司
珠海万通特种工程塑料有限公司
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Publication of WO2023005726A1 publication Critical patent/WO2023005726A1/en

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    • 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
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • 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
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/08—Oxygen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • 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
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • 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
    • C08K2201/011—Nanostructured 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

Definitions

  • the invention relates to the technical field of polymer materials, in particular to an antistatic polyamide composition and its preparation method and application.
  • the imaging system is rapidly popularized in daily life.
  • the key to the imaging system is the lens.
  • lenses such as mobile phone camera module lenses, laptop/AIO all-in-one machine lenses, and monitoring lenses.
  • the current lens has been modularized, called a camera module, which is mainly composed of a lens, a voice coil motor, a photosensitive chip, a sensor, an infrared filter, and a circuit board.
  • the plastic lens bracket needs to have the following characteristics: heat resistance, adhesiveness, dimensional stability, formability, low dust generation, and surface smoothness.
  • the imaging effect of the camera will continue to decrease with the prolongation of use time.
  • the main reason is that the lens is polluted by granular dust (size greater than 10 ⁇ m), which mainly comes from two
  • one is the external dust caused by the poor packaging of the module, and this kind of dust pollution is closely related to the electrostatic dust absorption effect of the insulating plastic material in the module.
  • Another important source is that the plastic lens holder is vibrated or driven. The particles that fall out due to friction (the main component is the filler in it), therefore, as a lens holder material, it should have the highest possible anti-static dust absorption and low self-dusting characteristics to keep the lens clean for a long time.
  • the plastic material lens bracket not only plays a role of supporting the lens, but also plays a role of transmission support when the lens expands and contracts.
  • the surface smoothness of the material has an important influence on the lubrication and wear resistance characteristics during the transmission movement , Therefore, the material is required to have high surface smoothness in order to obtain excellent lubrication and wear resistance.
  • workpieces with uneven surfaces are prone to drop tiny particles during long-term use. Therefore, surface smoothness is also closely related to low dust generation.
  • heat resistance, adhesiveness, dimensional stability, and molding performance can be satisfied by the optimization of matrix resin or other means, and high surface smoothness can be adjusted by plastic filling substances.
  • high surface smoothness and low dust generation at the same time is still a difficult problem in the industry, which involves the self-dust generation and electrostatic dust collection properties of the material.
  • the object of the present invention is to overcome the above-mentioned technical defects, and provide an antistatic polyamide composition, which has the advantages of smooth surface, good antistatic dust absorption and dust generation resistance.
  • Another object of the present invention is to provide the preparation method and application of the above antistatic polyamide composition.
  • An antistatic polyamide composition by weight, comprises the following components:
  • the mineral fiber is selected from at least one of wollastonite fiber, calcium sulfate fiber, calcium silicate fiber, aluminum silicate fiber and sepiolite fiber.
  • the polyamide resin is selected from at least one of semi-aromatic polyamide and aliphatic polyamide; the semi-aromatic polyamide is selected from PA6T/66, PA6I, PA6T/6I, PA6T/M5T, PA9T, PA9T/ 66. At least one of PA10T, PA10T/66, PA10T/10I, PA10T/1010, PA12T, PA12I; the aliphatic polyamide is selected from PA6, PA66, PA610, PA612, PA1010, PA1012, PA1212, PA11, At least one of PA12.
  • the present invention has no special requirement on the weight-average molecular weight of the polyamide resin. Generally speaking, the purpose of the present invention can be achieved if the weight-average molecular weight is within the range of 5000-100000 g/mol.
  • the polyamide resin of the present invention can be selected from pure aliphatic polyamide, pure semi-aromatic polyamide, a combination of aliphatic polyamide and semi-aromatic polyamide resin.
  • the combination of aliphatic polyamide and semi-aromatic polyamide resin or pure semi-aromatic polyamide preferably, based on the total weight of polyamide resin, semi-aromatic polyamide is 75-100wt%, and aliphatic polyamide is 0-100wt%. 25 wt%; more preferably, based on the total weight of polyamide resin, semi-aromatic polyamide is 85-100 wt%, and aliphatic polyamide is 0-15 wt%.
  • the average diameter of the isotropic pitch-based carbon fibers is 2-20 microns; preferably, the average diameter of the isotropic pitch-based carbon fibers is 12-14 microns.
  • the nanostructure carbon is selected from at least one of single-arm carbon nanotubes, multi-arm carbon nanotubes, and bifurcated array carbon nanostructures; preferably, the nanostructure carbon is selected from multi-arm carbon nanostructures. Tube.
  • the percolation structure network formed by the preferred nanostructured carbon is better, and at the same time, the surface smoothness of the antistatic polyamide composition is better, and self-grinding dust is not easy to be generated after long-term use.
  • nano-conductive carbon materials also include graphene, graphyne, C60, nano-carbon black, and the like.
  • the dispersibility of the above-mentioned nano-conductive carbon material is not as good as that of nano-structured carbon, thereby reducing the surface smoothness of the workpiece, and self-wearing dust will be generated after long-term use.
  • the nano-dimensional size of the nano-structured carbon is 0.5-50 nanometers.
  • the meaning of the nano-dimensional size is: the size range of the nano-dimensional in the three dimensions of the nano-object (for an object, the shape and size of the material can be defined through the three spatial dimensions, and for nano-scale materials, the nano-scale The concept does not require all three dimensions to reach the nanometer level, only one of the dimensions needs to reach the nanometer level to be called a nanomaterial). Such as average diameter, diameter, average thickness, thickness, length, average length, particle size, average particle size, etc.
  • the average diameter of the mineral fibers is 0.5-15 microns; preferably, the average diameter of the mineral fibers is 2-8 microns; preferably, the mineral fibers are selected from calcium sulfate fibers.
  • the volume resistivity value of the antistatic polyamide composition of the present invention is less than or equal to 9.9 ⁇ 10 8 ohm ⁇ cm.
  • antioxidants and UV-resistant agents can be added according to actual needs to improve oxidation resistance, UV resistance, etc.
  • the antioxidant can be antioxidant 1010, etc., and technicians can choose the type of antioxidant to add according to the actual situation.
  • the polyamide resin and nano-structured carbon are uniformly mixed according to the ratio, and then added to the main feeding port of the twin-screw extruder, and the isotropic pitch-based carbon fiber is fed through the first side.
  • the feeder is added to the twin-screw extruder, and the mineral fiber is added to the twin-screw extruder through the second side feeder, melted, extruded, and granulated to obtain an antistatic polyamide composition; wherein, the screw speed range is 200 ⁇ 500rpm, aspect ratio is 40:1 ⁇ 48:1, temperature range is 270-320°C.
  • the application of the antistatic polyamide composition of the present invention is used for preparing camera module components.
  • the present invention has the following beneficial effects
  • the existing technology mainly forms the percolation structure network required for antistatic by compounding a certain amount of carbon fiber and nano-structured carbon (or other nano-conductive carbon materials).
  • carbon fiber content is too high, it will cause floating fiber defects due to its large microscopic size and excellent heat transfer characteristics; if the nanostructured carbon (or other nano-conductive carbon materials) (or other nano-conductive carbon materials) too much internal air entrainment and agglomeration will cause the surface of the part to be uneven, which will easily cause self-dusting, and will also lead to the destruction of the percolation structure network.
  • the present invention increases the viscosity of the system by adding mineral fibers, so that the screw rod can effectively transmit the shearing effect on the melt of the composition during extrusion processing, so that the filler (isotropic pitch-based carbon fiber, nano Structural carbon, mineral fibers) dispersion/distribution is significantly better. It can not only make the isotropic pitch-based carbon fiber and nano-structure carbon form a good percolation structure network at a low content, but also inhibit the damage to surface smoothness at a high content of the isotropic pitch-based carbon fiber and nano-structure carbon.
  • the raw material sources used in the present invention are as follows:
  • PA6T/66 Vicnyl 4X, Kingfa Science & Technology Co., Ltd., weight average molecular weight 30000g/mol;
  • PA10T Vicnyl 7X, Kingfa Science & Technology Co., Ltd., weight average molecular weight 10000g/mol;
  • PA10T/1010 Vicnyl 8X, Kingfa Science & Technology Co., Ltd., weight average molecular weight 7000g/mol;
  • PA66 PA66 EPR24, China Shenma Group, weight average molecular weight 20000g/mol;
  • PA612 Zytel 153HSL NC010, DuPont, USA, weight average molecular weight 100000g/mol;
  • PA12 Grilamid L 20HL, Swiss EMS company, weight average molecular weight 70000g/mol;
  • Calcium sulfate fiber A DL-40H, average diameter 2 ⁇ m, Changzhou Guangwei New Material Co., Ltd.;
  • Calcium sulfate fiber B DL-30, with an average diameter of 4 ⁇ m, Changzhou Guangwei New Material Co., Ltd.;
  • Calcium sulfate fiber C DL-10, with an average diameter of 8 ⁇ m, Changzhou Guangwei New Material Co., Ltd.;
  • Calcium sulfate fiber D NP-M01, average diameter 0.7 ⁇ m, Jiangxi Fengzhu New Material Technology Co., Ltd.;
  • Calcium sulfate fiber E calcium sulfate whiskers, average diameter 14 ⁇ m, Jinan Qingyuyuan New Material Co., Ltd.;
  • Wollastonite fiber needle-shaped wollastonite, with an average diameter of 10 ⁇ m, Jiangxi Huajietai Mineral Fiber Technology Co., Ltd.;
  • Calcium silicate fiber MD1250-10012, average diameter 7 ⁇ m, Shanghai Huazhongrong Trading Co., Ltd.;
  • Aluminum silicate fiber aluminum silicate powder, diameter 7 ⁇ m, Shandong Minye Refractory Fiber Co., Ltd.;
  • Sepiolite fiber sepiolite fiber, diameter 15 ⁇ m, Shijiazhuang Huijin Mining Products Co., Ltd.;
  • Glass fiber EC11-3.0, round chopped glass fiber, with an average diameter of 10 ⁇ m, Bicheng Company, Taiwan province, China;
  • Magnesium sulfate fiber NP-YW2, average diameter 4 ⁇ m, Shanghai Fengzhu Composite New Material Technology Co., Ltd.;
  • Polycrystalline mullite fiber T-1600, average diameter 4 ⁇ m, Zhejiang Jiahua Crystal Fiber Co., Ltd.;
  • Alumina fiber T-1700, average diameter 4 ⁇ m, Zhejiang Jiahua Crystal Fiber Co., Ltd.;
  • Isotropic pitch-based carbon fiber A DONACARBO S-242, average diameter 13 ⁇ m, Osaka Gas Chemical Co., Ltd., Japan;
  • Isotropic pitch-based carbon fiber B DONACARBO S-344, average diameter 18 ⁇ m, Osaka Gas Chemical Co., Ltd., Japan;
  • Anisotropic pitch-based carbon fiber XN80, average diameter 11 ⁇ m, Japan Graphite Fiber Company;
  • PAN-based carbon fiber PX35CA0250-65, with an average diameter of 7 ⁇ m, Toray Corporation of Japan;
  • Single-armed carbon nanotubes TUBALL single-armed carbon nanotubes, with an average diameter of 2.0nm, Okosi Air Trading (Shenzhen) Co., Ltd.;
  • Multi-armed carbon nanotubes NANOCYL NC7000, average diameter 9.5nm, Belgian NANOCYL company;
  • Forked array carbon nanostructures CNS, average nano-dimensional size 5.0nm, Cabot Corporation;
  • Nano-scale carbon black nano-carbon black, average particle size 15nm, Cabot Corporation;
  • Graphene highly conductive graphene powder, flake shape, sheet thickness of 0.5nm, Deyang Carbon Technology Co., Ltd.;
  • Antioxidant Antioxidant 1010, BASF.
  • Examples and comparative examples The preparation method of the antistatic polyamide composition: mix the polyamide resin and nanostructure carbon evenly according to the proportion, then add the main feeding port of the twin-screw extruder, pass the isotropic pitch-based carbon fiber through the first The feeder on one side is fed into the twin-screw extruder, and the mineral fiber is fed into the twin-screw extruder through the second side feeder, melted, extruded, and granulated to obtain an antistatic polyamide composition; wherein, the rotational speed of the screw The range is 300-400rpm, the aspect ratio is 48:1, and the temperature range is 270-320°C.
  • Dust generation test The sample is injection molded into samples A and B of 40mm ⁇ 40mm ⁇ 1.0mm.
  • the sample test scene is as follows: (1) The dust generation test is carried out immediately within 2 hours after the injection molding is completed. This sample is called A Sample; (2) After being placed in a daily house (temperature 23°C, humidity 67%) for 168 hours, the dust generation test (to characterize the antistatic and dust-absorbing properties of the material), this sample is called B sample.
  • the dust generation rating is defined as follows : Grade 1 (excellent) is Fa ⁇ 5, Grade 2 (excellent) is 5 ⁇ Fa ⁇ 20, Grade 3 (good) is 20 ⁇ Fa ⁇ 35, Grade 4 (medium) is 35 ⁇ Fa ⁇ 50, Grade 5 (difference) is 50 ⁇ Fa.
  • the instrument model of the liquid particle counter is RION KS-42BF
  • the instrument model of the ultrasonic cleaner is BK-240J.
  • grades 1-3 are qualified, and grades 1 and 2 belong to the low self-dusting level.
  • volume resistivity measured with reference to IEC 60093-1980, the material sample (100mm ⁇ 100mm ⁇ 2.0mm) was kept under 500V DC for 1 minute, and the current passing through the sample material was measured, and calculated to obtain the material Volume resistivity, in ohm cm.
  • Example 1 Example 2
  • Example 3 Example 4
  • PA6T/66 60 the the the the PA10T the 60 the the PA10T/1010 the the 60 the the PA66 the the the 60 the PA612 the the the the 60 PA12 the the the the the
  • Example 6 Example 7
  • Example 8 Example 9
  • Example 10 Example 11 PA6T/66 the the the the 45 the PA10T 59 51 45 39 the the PA10T/1010 the the the the the 45 PA66 the the the the 15 the PA612 1 9 15 twenty one the the PA12 the the the the the 15 Isotropic pitch-based carbon fiber
  • a 10 10 10 10 10 10 10 10 10 10 10 Calcium Sulfate Fiber
  • the average diameter of the mineral fibers is preferably in the range of 2-8 microns.
  • Example 8/21 It can be known from Example 8/21 that the preferred antistatic polyamide composition of isotropic pitch-based carbon fibers has a lower volume resistivity.
  • Comparative example 8 Comparative example 9 Comparative example 10 Comparative example 11
  • PA612 15 15 15 15 Isotropic pitch-based carbon fiber
  • a sample level 2 level 2
  • Level 5 level 4 Level 5 level 4 Volume resistivity, ohm cm 8.1 ⁇ 10 11 4.8 ⁇ 10 9 1.3 ⁇ 10 10 6.1 ⁇ 10 9 Surface roughness, ⁇ m 0.16 0.21 0.12 0.27

Abstract

Disclosed in the present invention is an antistatic polyamide composition that comprises, in parts by weight, the following components: 60 parts of a polyamide resin, 2-18 parts of isotropic pitch-based carbon fibers, 10-40 parts of mineral fibers, and 0.05-5 parts of nano-structure carbon, wherein the mineral fibers are selected from at least one of wollastonite fibers, calcium sulfate fibers, calcium silicate fibers, aluminum silicate fibers, and sepiolite fibers. By compounding the isotropic pitch-based carbon fibers, the mineral fibers, and the nano-structure carbon, defects on the surface of a workpiece can be effectively reduced, and a good antistatic dust-absorbing property and spontaneous dust resistance can also be achieved.

Description

一种抗静电聚酰胺组合物及其制备方法和应用A kind of antistatic polyamide composition and its preparation method and application 技术领域technical field
本发明涉及高分子材料技术领域，特别是涉及一种抗静电聚酰胺组合物及其制备方法和应用。The invention relates to the technical field of polymer materials, in particular to an antistatic polyamide composition and its preparation method and application.
背景技术Background technique
随着现代科技技术的发展，成像***在日常生活中急速普及，成像***的关键为镜头，镜头的品种各式各样，如手机照相机模组镜头、笔记本电脑/AIO一体机镜头、监控用镜头、车载镜头、扫描仪镜头、多媒体电视内置摄像头镜头等。目前的镜头均已模块化，称为摄像头模组，主要由镜头、音圈马达、感光芯片、传感器、红外线滤光片及电路板等部件组成。With the development of modern technology, the imaging system is rapidly popularized in daily life. The key to the imaging system is the lens. There are various types of lenses, such as mobile phone camera module lenses, laptop/AIO all-in-one machine lenses, and monitoring lenses. , Car lens, scanner lens, multimedia TV built-in camera lens, etc. The current lens has been modularized, called a camera module, which is mainly composed of a lens, a voice coil motor, a photosensitive chip, a sensor, an infrared filter, and a circuit board.
塑料镜头支架作为摄像头模组的重要组成部分，需要具备如下特点：耐热性、粘接性、尺寸稳定性、成型性、低发尘性、表面平滑性。As an important part of the camera module, the plastic lens bracket needs to have the following characteristics: heat resistance, adhesiveness, dimensional stability, formability, low dust generation, and surface smoothness.
在使用的过程中，摄像头的成像效果将会随着使用时间的加长而清晰度不断下降，主要原因是镜头受到了颗粒状粉尘的污染(尺寸大于10μm)，此类颗粒状粉尘主要来源于两方面，其一为因模组封装不严导致的外部粉尘，而此类粉尘污染与模组中的绝缘塑料材料静电吸尘作用有较大关联，另一重要来源为塑料镜头支架受震动或者传动摩擦而掉落出来的颗粒(主要成分为其中的填充物)，因此，作为镜头支架材料，应该具备尽可能高的抗静电吸尘及低的自发尘特性以较长时间保持镜头的清洁。In the process of use, the imaging effect of the camera will continue to decrease with the prolongation of use time. The main reason is that the lens is polluted by granular dust (size greater than 10 μm), which mainly comes from two On the one hand, one is the external dust caused by the poor packaging of the module, and this kind of dust pollution is closely related to the electrostatic dust absorption effect of the insulating plastic material in the module. Another important source is that the plastic lens holder is vibrated or driven. The particles that fall out due to friction (the main component is the filler in it), therefore, as a lens holder material, it should have the highest possible anti-static dust absorption and low self-dusting characteristics to keep the lens clean for a long time.
关于表面平滑性，一方面，塑料材料镜头支架不仅起到镜头的支撑作用，在镜头伸缩时也起到了传动支撑作用，材料的表面平滑性对传动运动过程中的润滑耐磨特性有重要的影响，因此，要求材料具有高的表面平滑性以获得优异的润滑耐磨性。另一方面，表面不平滑的制件在长时间的使用过程中很容易掉落微小颗粒。因此，表面平滑性也与低发尘性密切相关。Regarding the smoothness of the surface, on the one hand, the plastic material lens bracket not only plays a role of supporting the lens, but also plays a role of transmission support when the lens expands and contracts. The surface smoothness of the material has an important influence on the lubrication and wear resistance characteristics during the transmission movement , Therefore, the material is required to have high surface smoothness in order to obtain excellent lubrication and wear resistance. On the other hand, workpieces with uneven surfaces are prone to drop tiny particles during long-term use. Therefore, surface smoothness is also closely related to low dust generation.
其中，耐热性、粘接性、尺寸稳定性、成型性能通过基体树脂的优选或其他手段进行满足，高表面平滑性可通过塑料填充物质进行表面调节。但是，同时实现高表面平滑性与低发尘性则仍为业界难题，其中涉及材料的自发尘性和静电吸尘性。Among them, heat resistance, adhesiveness, dimensional stability, and molding performance can be satisfied by the optimization of matrix resin or other means, and high surface smoothness can be adjusted by plastic filling substances. However, achieving high surface smoothness and low dust generation at the same time is still a difficult problem in the industry, which involves the self-dust generation and electrostatic dust collection properties of the material.
发明内容Contents of the invention
本发明的目的在于，克服上述技术缺陷，提供一种抗静电聚酰胺组合物，具有表面平滑性，并且抗静电吸尘性、抗发尘性良好的优点。The object of the present invention is to overcome the above-mentioned technical defects, and provide an antistatic polyamide composition, which has the advantages of smooth surface, good antistatic dust absorption and dust generation resistance.
本发明的另一目的在于，提供上述抗静电聚酰胺组合物的制备方法和应用。Another object of the present invention is to provide the preparation method and application of the above antistatic polyamide composition.
本发明是通过以下技术方案实现的：The present invention is achieved through the following technical solutions:
一种抗静电聚酰胺组合物，按重量份计，包括以下组分：An antistatic polyamide composition, by weight, comprises the following components:
Figure PCTCN2022106378-appb-000001
Figure PCTCN2022106378-appb-000001
所述的矿物纤维选自硅灰石纤维、硫酸钙纤维、硅酸钙纤维、硅酸铝纤维、海泡石纤维中的至少一种。The mineral fiber is selected from at least one of wollastonite fiber, calcium sulfate fiber, calcium silicate fiber, aluminum silicate fiber and sepiolite fiber.
所述的聚酰胺树脂选自半芳香聚酰胺、脂肪族聚酰胺中的至少一种；所述的半芳香聚酰胺选自PA6T/66、PA6I、PA6T/6I、PA6T/M5T、PA9T、PA9T/66、PA10T、PA10T/66、PA10T/10I、PA10T/1010、PA12T、PA12I中的至少一种；所述的脂肪族聚酰胺选自PA6、PA66、PA610、PA612、PA1010、PA1012、PA1212、PA11、PA12中的至少一种。The polyamide resin is selected from at least one of semi-aromatic polyamide and aliphatic polyamide; the semi-aromatic polyamide is selected from PA6T/66, PA6I, PA6T/6I, PA6T/M5T, PA9T, PA9T/ 66. At least one of PA10T, PA10T/66, PA10T/10I, PA10T/1010, PA12T, PA12I; the aliphatic polyamide is selected from PA6, PA66, PA610, PA612, PA1010, PA1012, PA1212, PA11, At least one of PA12.
本发明对于聚酰胺树脂的重均分子量没有特别的要求，一般来说重均分子量在5000-100000g/mol范围内都可以实现本发明的目的。The present invention has no special requirement on the weight-average molecular weight of the polyamide resin. Generally speaking, the purpose of the present invention can be achieved if the weight-average molecular weight is within the range of 5000-100000 g/mol.
本发明的聚酰胺树脂可以选用纯脂肪族聚酰胺、纯半芳香族聚酰胺、脂肪族聚酰胺与半芳香族聚酰胺树脂的组合。当选用脂肪族聚酰胺与半芳香族聚酰胺树脂的组合或者纯半芳香族聚酰胺时，优选，以聚酰胺树脂的总重量计，半芳香聚酰胺75-100wt％，脂肪族聚酰胺0-25wt％；更优选的，以聚酰胺树脂的总重量计，半芳香聚酰胺85-100wt％，脂肪族聚酰胺0-15wt％。The polyamide resin of the present invention can be selected from pure aliphatic polyamide, pure semi-aromatic polyamide, a combination of aliphatic polyamide and semi-aromatic polyamide resin. When selecting the combination of aliphatic polyamide and semi-aromatic polyamide resin or pure semi-aromatic polyamide, preferably, based on the total weight of polyamide resin, semi-aromatic polyamide is 75-100wt%, and aliphatic polyamide is 0-100wt%. 25 wt%; more preferably, based on the total weight of polyamide resin, semi-aromatic polyamide is 85-100 wt%, and aliphatic polyamide is 0-15 wt%.
所述的各项同性沥青系碳纤维的平均直径为2-20微米；优选的，所述的各项同性沥青系碳纤维的平均直径为12-14微米。The average diameter of the isotropic pitch-based carbon fibers is 2-20 microns; preferably, the average diameter of the isotropic pitch-based carbon fibers is 12-14 microns.
所述的纳米结构碳选自单臂碳纳米管、多臂碳纳米管、分叉状阵列型碳纳米结构物中的至少一种；优选的，所述的纳米结构碳选自多臂碳纳米管。优选的纳米结构碳形成的逾渗结构网络更优，同时抗静电聚酰胺组合物制件的表面平滑性更好，长时间使用也不容易产生自磨粉尘。The nanostructure carbon is selected from at least one of single-arm carbon nanotubes, multi-arm carbon nanotubes, and bifurcated array carbon nanostructures; preferably, the nanostructure carbon is selected from multi-arm carbon nanostructures. Tube. The percolation structure network formed by the preferred nanostructured carbon is better, and at the same time, the surface smoothness of the antistatic polyamide composition is better, and self-grinding dust is not easy to be generated after long-term use.
现有技术中，作为纳米导电碳材料除了上述纳米结构碳外，还包括石墨烯、石墨炔、C60、纳米炭黑等。但是在本发明体系中上述纳米导电碳材料的分散性不如纳米结构碳，因而会降低制件的表面平滑性，长时间使用会产生自磨损粉尘。In the prior art, in addition to the above-mentioned nanostructured carbon, nano-conductive carbon materials also include graphene, graphyne, C60, nano-carbon black, and the like. However, in the system of the present invention, the dispersibility of the above-mentioned nano-conductive carbon material is not as good as that of nano-structured carbon, thereby reducing the surface smoothness of the workpiece, and self-wearing dust will be generated after long-term use.
优选的，所述的纳米结构碳的纳米维度尺寸为0.5～50纳米。Preferably, the nano-dimensional size of the nano-structured carbon is 0.5-50 nanometers.
纳米维度尺寸的含义为：该纳米物3个维度中达到纳米维度的尺寸范围(对一个物体而言，通过3个空间维度可以定义出材料的形状大小，而对于纳米级材料而言，纳米的概念并 不需要3个维度都达到纳米级，只需要其中一个维度尺寸达到纳米级即可称之为纳米材料)。如平均直径、直径、平均厚度、厚度、长度、平均长度、粒径、平均粒径等。The meaning of the nano-dimensional size is: the size range of the nano-dimensional in the three dimensions of the nano-object (for an object, the shape and size of the material can be defined through the three spatial dimensions, and for nano-scale materials, the nano-scale The concept does not require all three dimensions to reach the nanometer level, only one of the dimensions needs to reach the nanometer level to be called a nanomaterial). Such as average diameter, diameter, average thickness, thickness, length, average length, particle size, average particle size, etc.
所述矿物纤维的平均直径是0.5-15微米；优选的，所述矿物纤维的平均直径是2-8微米；优选的，所述的矿物纤维选自硫酸钙纤维。The average diameter of the mineral fibers is 0.5-15 microns; preferably, the average diameter of the mineral fibers is 2-8 microns; preferably, the mineral fibers are selected from calcium sulfate fibers.
本发明的抗静电聚酰胺组合物的体积电阻率值小于等于9.9×10 8ohm·cm。 The volume resistivity value of the antistatic polyamide composition of the present invention is less than or equal to 9.9×10 8 ohm·cm.
可以根据实际需求添加0-2份的抗氧剂、耐紫外线剂以提升抗氧化性、耐紫外线性等。0-2 parts of antioxidants and UV-resistant agents can be added according to actual needs to improve oxidation resistance, UV resistance, etc.
抗氧剂可以是抗氧剂1010等，技术人员可根据实际情况选择抗氧剂种类添加。The antioxidant can be antioxidant 1010, etc., and technicians can choose the type of antioxidant to add according to the actual situation.
本发明的抗静电聚酰胺组合物的制备方法，按照配比聚酰胺树脂、纳米结构碳混合均匀，再加入双螺杆挤出机主喂料口，将各项同性沥青系碳纤维通过第一侧喂料机加入双螺杆挤出机，将矿物纤维通过第二侧喂料机加入双螺杆挤出机，熔融挤出、造粒，即得到抗静电聚酰胺组合物；其中，螺杆的转速范围是200～500rpm，长径比是40:1～48:1，温度范围是270-320℃。According to the preparation method of the antistatic polyamide composition of the present invention, the polyamide resin and nano-structured carbon are uniformly mixed according to the ratio, and then added to the main feeding port of the twin-screw extruder, and the isotropic pitch-based carbon fiber is fed through the first side. The feeder is added to the twin-screw extruder, and the mineral fiber is added to the twin-screw extruder through the second side feeder, melted, extruded, and granulated to obtain an antistatic polyamide composition; wherein, the screw speed range is 200 ～500rpm, aspect ratio is 40:1～48:1, temperature range is 270-320℃.
本发明的抗静电聚酰胺组合物的应用，用于制备摄像头模组部件。The application of the antistatic polyamide composition of the present invention is used for preparing camera module components.
本发明与现有技术相比，具有如下有益效果Compared with the prior art, the present invention has the following beneficial effects
为了实现良好的抗静电性能，现有技术主要是通过复配一定含量的碳纤维和纳米结构碳(或其他纳米导电碳材料)形成抗静电所需的逾渗结构网络。但是，如果碳纤维含量过高，因其较大的微观尺寸和极其优异的传热特性会导致浮纤缺陷；如果纳米结构碳(或其他纳米导电碳材料)含量过高，也会因为纳米结构碳(或其他纳米导电碳材料)内部夹气过多以及团聚现象导致制件表面不平滑，容易带来自发尘，也会导致逾渗结构网络被破坏。In order to achieve good antistatic performance, the existing technology mainly forms the percolation structure network required for antistatic by compounding a certain amount of carbon fiber and nano-structured carbon (or other nano-conductive carbon materials). However, if the carbon fiber content is too high, it will cause floating fiber defects due to its large microscopic size and excellent heat transfer characteristics; if the nanostructured carbon (or other nano-conductive carbon materials) (or other nano-conductive carbon materials) too much internal air entrainment and agglomeration will cause the surface of the part to be uneven, which will easily cause self-dusting, and will also lead to the destruction of the percolation structure network.
为了解决上述技术缺陷，本发明通过添加矿物纤维来提高体系的粘度，使组合物在挤出加工时螺杆对其熔体剪切作用得到有效传递，使填充物(各项同性沥青系碳纤维、纳米结构碳、矿物纤维)分散/分布情况显著变好。既能够使各项同性沥青系碳纤维和纳米结构碳在低含量下形成良好的逾渗结构网络，也能够抑制各项同性沥青系碳纤维和纳米结构碳高含量下对表面平滑性的破坏。In order to solve the above-mentioned technical defects, the present invention increases the viscosity of the system by adding mineral fibers, so that the screw rod can effectively transmit the shearing effect on the melt of the composition during extrusion processing, so that the filler (isotropic pitch-based carbon fiber, nano Structural carbon, mineral fibers) dispersion/distribution is significantly better. It can not only make the isotropic pitch-based carbon fiber and nano-structure carbon form a good percolation structure network at a low content, but also inhibit the damage to surface smoothness at a high content of the isotropic pitch-based carbon fiber and nano-structure carbon.
具体实施方式Detailed ways
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。The present invention will be described in detail below in conjunction with specific embodiments. The following examples will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be noted that those skilled in the art can make several modifications and improvements without departing from the concept of the present invention. These all belong to the protection scope of the present invention.
本发明所用原材料来源如下：The raw material sources used in the present invention are as follows:
PA6T/66：Vicnyl 4X，金发科技股份有限公司，重均分子量30000g/mol；PA6T/66: Vicnyl 4X, Kingfa Science & Technology Co., Ltd., weight average molecular weight 30000g/mol;
PA10T：Vicnyl 7X，金发科技股份有限公司，重均分子量10000g/mol；PA10T: Vicnyl 7X, Kingfa Science & Technology Co., Ltd., weight average molecular weight 10000g/mol;
PA10T/1010：Vicnyl 8X，金发科技股份有限公司，重均分子量7000g/mol；PA10T/1010: Vicnyl 8X, Kingfa Science & Technology Co., Ltd., weight average molecular weight 7000g/mol;
PA66：PA66 EPR24，中国神马集团，重均分子量20000g/mol；PA66: PA66 EPR24, China Shenma Group, weight average molecular weight 20000g/mol;
PA612：Zytel 153HSL NC010，美国杜邦公司，重均分子量100000g/mol；PA612: Zytel 153HSL NC010, DuPont, USA, weight average molecular weight 100000g/mol;
PA12：Grilamid L 20HL，瑞士EMS公司，重均分子量70000g/mol；PA12: Grilamid L 20HL, Swiss EMS company, weight average molecular weight 70000g/mol;
硫酸钙纤维A：DL-40H，平均直径2μm，常州广威新材料公司；Calcium sulfate fiber A: DL-40H, average diameter 2μm, Changzhou Guangwei New Material Co., Ltd.;
硫酸钙纤维B：DL-30，平均直径4μm，常州广威新材料公司；Calcium sulfate fiber B: DL-30, with an average diameter of 4 μm, Changzhou Guangwei New Material Co., Ltd.;
硫酸钙纤维C：DL-10，平均直径8μm，常州广威新材料公司；Calcium sulfate fiber C: DL-10, with an average diameter of 8 μm, Changzhou Guangwei New Material Co., Ltd.;
硫酸钙纤维D：NP-M01，平均直径0.7μm，江西峰竺新材料科技有限公司；Calcium sulfate fiber D: NP-M01, average diameter 0.7μm, Jiangxi Fengzhu New Material Technology Co., Ltd.;
硫酸钙纤维E：硫酸钙晶须，平均直径14μm，济南青玉元新材料有限公司；Calcium sulfate fiber E: calcium sulfate whiskers, average diameter 14μm, Jinan Qingyuyuan New Material Co., Ltd.;
硅灰石纤维：针状硅灰石，平均直径10μm，江西华杰泰矿纤科技有限公司；Wollastonite fiber: needle-shaped wollastonite, with an average diameter of 10 μm, Jiangxi Huajietai Mineral Fiber Technology Co., Ltd.;
硅酸钙纤维：MD1250-10012，平均直径7μm，上海华仲荣贸易有限公司；Calcium silicate fiber: MD1250-10012, average diameter 7μm, Shanghai Huazhongrong Trading Co., Ltd.;
硅酸铝纤维：硅酸铝粉，直径7μm，山东民烨耐火纤维有限公司；Aluminum silicate fiber: aluminum silicate powder, diameter 7μm, Shandong Minye Refractory Fiber Co., Ltd.;
海泡石纤维：海泡石纤维，直径15μm，石家庄汇锦矿产品有限公司；Sepiolite fiber: sepiolite fiber, diameter 15μm, Shijiazhuang Huijin Mining Products Co., Ltd.;
[根据细则91更正 25.08.2022]　
玻璃纤维：EC11-3.0，圆形短切玻纤，平均直径10μm，中国台湾省必成公司；[Corrected 25.08.2022 under Rule 91]
Glass fiber: EC11-3.0, round chopped glass fiber, with an average diameter of 10 μm, Bicheng Company, Taiwan Province, China;
硫酸镁纤维：NP-YW2，平均直径4μm，上海峰竺复合新材料科技有限公司；Magnesium sulfate fiber: NP-YW2, average diameter 4μm, Shanghai Fengzhu Composite New Material Technology Co., Ltd.;
多晶莫来石纤维：T-1600，平均直径4μm，浙江嘉华晶体纤维有限公司；Polycrystalline mullite fiber: T-1600, average diameter 4μm, Zhejiang Jiahua Crystal Fiber Co., Ltd.;
氧化铝纤维：T-1700，平均直径4μm，浙江嘉华晶体纤维有限公司；Alumina fiber: T-1700, average diameter 4μm, Zhejiang Jiahua Crystal Fiber Co., Ltd.;
各项同性沥青系碳纤维A：DONACARBO S-242，平均直径13μm，日本大阪燃气化学公司；Isotropic pitch-based carbon fiber A: DONACARBO S-242, average diameter 13 μm, Osaka Gas Chemical Co., Ltd., Japan;
各项同性沥青系碳纤维B：DONACARBO S-344，平均直径18μm，日本大阪燃气化学公司；Isotropic pitch-based carbon fiber B: DONACARBO S-344, average diameter 18 μm, Osaka Gas Chemical Co., Ltd., Japan;
各向异性沥青系碳纤维：XN80，平均直径11μm，日本石墨纤维公司；Anisotropic pitch-based carbon fiber: XN80, average diameter 11μm, Japan Graphite Fiber Company;
PAN系碳纤维：PX35CA0250-65，平均直径7μm，日本东丽公司；PAN-based carbon fiber: PX35CA0250-65, with an average diameter of 7 μm, Toray Corporation of Japan;
单臂碳纳米管：TUBALL单臂碳纳米管，平均直径2.0nm，奥科希艾尔贸易(深圳)有限公司；Single-armed carbon nanotubes: TUBALL single-armed carbon nanotubes, with an average diameter of 2.0nm, Okosi Air Trading (Shenzhen) Co., Ltd.;
多臂碳纳米管：NANOCYL NC7000，平均直径9.5nm，比利时NANOCYL公司；Multi-armed carbon nanotubes: NANOCYL NC7000, average diameter 9.5nm, Belgian NANOCYL company;
分叉状阵列碳纳米结构物：CNS，平均纳米维度尺寸5.0nm，卡博特公司；Forked array carbon nanostructures: CNS, average nano-dimensional size 5.0nm, Cabot Corporation;
石墨炔：平均厚度3nm，中科院化学所；Graphdiyne: average thickness 3nm, Institute of Chemistry, Chinese Academy of Sciences;
C60：富勒烯C60，平均粒径0.71nm，上海皓鸿生物医药科技有限公司；C60: Fullerene C60, average particle size 0.71nm, Shanghai Haohong Biomedical Technology Co., Ltd.;
纳米级炭黑：纳米炭黑，平均粒径15nm，卡博特公司；Nano-scale carbon black: nano-carbon black, average particle size 15nm, Cabot Corporation;
石墨烯：高导电型石墨烯粉体，片状形貌，片层厚度为0.5nm，德阳烯碳科技有限公司；Graphene: highly conductive graphene powder, flake shape, sheet thickness of 0.5nm, Deyang Carbon Technology Co., Ltd.;
抗氧剂：抗氧剂1010，巴斯夫公司。Antioxidant: Antioxidant 1010, BASF.
实施例和对比例抗静电聚酰胺组合物的制备方法：按照配比将聚酰胺树脂、纳米结构碳混合均匀，再加入双螺杆挤出机主喂料口，将各项同性沥青系碳纤维通过第一侧喂料机加入双螺杆挤出机，将矿物纤维通过第二侧喂料机加入双螺杆挤出机，熔融挤出、造粒，即得到抗静电聚酰胺组合物；其中，螺杆的转速范围是300-400rpm，长径比是48:1，温度范围是270-320℃。Examples and comparative examples The preparation method of the antistatic polyamide composition: mix the polyamide resin and nanostructure carbon evenly according to the proportion, then add the main feeding port of the twin-screw extruder, pass the isotropic pitch-based carbon fiber through the first The feeder on one side is fed into the twin-screw extruder, and the mineral fiber is fed into the twin-screw extruder through the second side feeder, melted, extruded, and granulated to obtain an antistatic polyamide composition; wherein, the rotational speed of the screw The range is 300-400rpm, the aspect ratio is 48:1, and the temperature range is 270-320°C.
测试方法：Test Methods:
(1)发尘性测试：将样品注塑为40mm×40mm×1.0mm的样板A、B，样板测试场景如下：(1)刚完成注塑后2h内立即进行发尘性测试，此样品称为A样板；(2)放置于日常房屋(温度23℃，湿度67％)中168h后进行发尘性测试(表征材料的抗静电吸尘性)，此样品称为B样板。将样板放置于由烧杯承装的500mL去离子水中，将装有样品的烧杯放入超声波清洗机，洗涤后(超声频率40kHz，时间A板20分钟，B板2分钟)，将清洗过样板的去离子水取出并置于液体池中，在23℃下用液体粒子计数器测试5min，使用软件程序统计直径大于10μm的粉尘的数量Fa，作为材料发尘性的表征参数，发尘性评级定义如下：1级(极优)为Fa＜5，2级(优)为5≤Fa＜20，3级(良)为20≤Fa＜35，4级(中)为35≤Fa＜50，5级(差)为50≤Fa。其中液体粒子计数器的仪器型号为RION KS-42BF，超声波清洗机的仪器型号为BK-240J。其中，1-3级合格，1级和2级属于低自发尘水平。(1) Dust generation test: The sample is injection molded into samples A and B of 40mm×40mm×1.0mm. The sample test scene is as follows: (1) The dust generation test is carried out immediately within 2 hours after the injection molding is completed. This sample is called A Sample; (2) After being placed in a daily house (temperature 23°C, humidity 67%) for 168 hours, the dust generation test (to characterize the antistatic and dust-absorbing properties of the material), this sample is called B sample. Place the template in 500mL of deionized water contained in a beaker, put the beaker containing the sample into an ultrasonic cleaner, and after washing (ultrasonic frequency 40kHz, time A board 20 minutes, B board 2 minutes), clean the sample Take out the deionized water and place it in a liquid pool, test it with a liquid particle counter at 23°C for 5 minutes, use a software program to count the number Fa of dust with a diameter greater than 10 μm, and use it as a characteristic parameter of the dust generation of the material. The dust generation rating is defined as follows : Grade 1 (excellent) is Fa<5, Grade 2 (excellent) is 5≤Fa<20, Grade 3 (good) is 20≤Fa<35, Grade 4 (medium) is 35≤Fa<50, Grade 5 (difference) is 50≤Fa. Among them, the instrument model of the liquid particle counter is RION KS-42BF, and the instrument model of the ultrasonic cleaner is BK-240J. Among them, grades 1-3 are qualified, and grades 1 and 2 belong to the low self-dusting level.
(2)体积电阻率：参照IEC 60093-1980进行测定，将材料样板(100mm×100mm×2.0mm)在500V直流电下保持1分钟，并测量通过该样板材料的电流，并以此计算获得材料的体积电阻率，单位为ohm·cm。(2) Volume resistivity: measured with reference to IEC 60093-1980, the material sample (100mm×100mm×2.0mm) was kept under 500V DC for 1 minute, and the current passing through the sample material was measured, and calculated to obtain the material Volume resistivity, in ohm cm.
(3)表面粗糙度：参照GB/T 1031-2009进行测定，使用轮廓法测试40mm×40mm×1.0mm的注塑样板的表面粗糙度，采用中线制(轮廓法)评定表面粗糙度，选取轮廓的算术平均偏差Ra值作为表征参数，取样基准长度lr优选为2.5mm，测量时选取5×lr的评定长度值，以保证测试的准确度，算术平均偏差Ra值的单位为μm。(3) Surface roughness: measure with reference to GB/T 1031-2009, use the contour method to test the surface roughness of the injection molded sample of 40mm×40mm×1.0mm, use the center line system (contour method) to evaluate the surface roughness, and select the contour The arithmetic mean deviation Ra value is used as a characterization parameter, the sampling reference length lr is preferably 2.5mm, and the evaluation length value of 5×lr is selected during measurement to ensure the accuracy of the test, and the unit of the arithmetic mean deviation Ra value is μm.
表1：实施例1-11抗静电聚酰胺组合物各组分含量(重量份)及测试结果Table 1: Contents (parts by weight) and test results of each component of the antistatic polyamide composition of Examples 1-11
 the 实施例1Example 1 实施例2Example 2 实施例3Example 3 实施例4Example 4 实施例5Example 5
PA6T/66PA6T/66 6060  the  the  the  the
PA10TPA10T  the 6060  the  the  the
PA10T/1010PA10T/1010  the  the 6060  the  the
PA66PA66  the  the  the 6060  the
PA612PA612  the  the  the  the 6060
PA12PA12  the  the  the  the  the
各项同性沥青系碳纤维AIsotropic pitch-based carbon fiber A 1010 1010 1010 1010 1010
硫酸钙纤维ACalcium Sulfate Fiber A 2020 2020 2020 2020 2020
单臂碳纳米管single-armed carbon nanotubes 22 22 22 22 22
抗氧剂antioxidant 0.30.3 0.30.3 0.30.3 0.30.3 0.30.3
发尘性测试(A样板)Dust generation test (A sample) 1级Level 1 1级Level 1 1级Level 1 2级level 2 2级level 2
发尘性测试(B样板)Dust generation test (B sample) 1级Level 1 1级Level 1 1级Level 1 1级Level 1 1级Level 1
体积电阻率，ohm·cmVolume resistivity, ohm cm 5.3×10 6 5.3×10 6 8.8×10 6 8.8×10 6 7.0×10 6 7.0×10 6 9.2×10 6 9.2×10 6 8.7×10 6 8.7×10 6
表面粗糙度，μmSurface roughness, μm 0.100.10 0.110.11 0.090.09 0.180.18 0.190.19
由实施例1-11可知，当采用脂肪族聚酰胺与半芳香族聚酰胺树脂的组合时，优选的半芳香、脂肪族配比内，抑制发尘性更好(自发尘、静电吸尘)，并且表面光滑度高(粗糙度低)。特别是，纯脂肪族聚酰胺组合物的表面粗糙度较高，这样会导致自抗发尘性稍差一些。It can be seen from Examples 1-11 that when a combination of aliphatic polyamide and semi-aromatic polyamide resin is used, the preferred semi-aromatic and aliphatic ratios have better dust generation suppression (self-dusting, electrostatic dust collection), And the surface smoothness is high (low roughness). In particular, pure aliphatic polyamide compositions have a higher surface roughness, which results in somewhat poorer self-dusting resistance.
续表1：Continuation of Table 1:
 the 实施例6Example 6 实施例7Example 7 实施例8Example 8 实施例9Example 9 实施例10Example 10 实施例11Example 11
PA6T/66PA6T/66  the  the  the  the 4545  the
PA10TPA10T 5959 5151 4545 3939  the  the
PA10T/1010PA10T/1010  the  the  the  the  the 4545
PA66PA66  the  the  the  the 1515  the
PA612PA612 11 99 1515 21twenty one  the  the
PA12PA12  the  the  the  the  the 1515
各项同性沥青系碳纤维AIsotropic pitch-based carbon fiber A 1010 1010 1010 1010 1010 1010
硫酸钙纤维ACalcium Sulfate Fiber A 2020 2020 2020 2020 2020 2020
单臂碳纳米管single-armed carbon nanotubes 22 22 22 22 22 22
抗氧剂antioxidant 0.30.3 0.30.3 0.30.3 0.30.3 0.30.3 0.30.3
发尘性测试(A样板)Dust generation test (A sample) 1级Level 1 1级Level 1 1级Level 1 1级Level 1 1级Level 1 1级Level 1
发尘性测试(B样板)Dust generation test (B sample) 1级Level 1 2级level 2 2级level 2 3级Level 3 2级level 2 2级level 2
体积电阻率，ohm·cmVolume resistivity, ohm cm 1.6×10 7 1.6×10 7 4.2×10 7 4.2×10 7 6.6×10 7 6.6×10 7 5.1×10 8 5.1×10 8 3.8×10 7 3.8×10 7 5.0×10 7 5.0×10 7
表面粗糙度，μmSurface roughness, μm 0.100.10 0.110.11 0.130.13 0.140.14 0.130.13 0.150.15
表2：实施例12-20抗静电聚酰胺组合物各组分含量(重量份)及测试结果Table 2: Contents (parts by weight) and test results of each component of the antistatic polyamide composition of Examples 12-20
Figure PCTCN2022106378-appb-000002
Figure PCTCN2022106378-appb-000002
Figure PCTCN2022106378-appb-000003
Figure PCTCN2022106378-appb-000003
由实施例8/12-15可知，优选矿物纤维的平均直径范围是微米2-8微米。From Examples 8/12-15, it can be known that the average diameter of the mineral fibers is preferably in the range of 2-8 microns.
由实施例8/16-20可知，随着各项同性沥青系碳纤维、单臂碳纳米管含量的增加，体积电阻率下降，但是表面粗糙度会上升，带来自发尘性的上升。It can be seen from Examples 8/16-20 that with the increase of the content of isotropic pitch-based carbon fibers and single-armed carbon nanotubes, the volume resistivity decreases, but the surface roughness increases, resulting in an increase in self-dust generation.
表3：实施例21-28抗静电聚酰胺组合物各组分含量(重量份)及测试结果Table 3: Contents (parts by weight) and test results of each component of the antistatic polyamide composition of Examples 21-28
Figure PCTCN2022106378-appb-000004
Figure PCTCN2022106378-appb-000004
由实施例8/21可知，优选的各项同性沥青系碳纤维的抗静电聚酰胺组合物的体积电阻率更低。It can be known from Example 8/21 that the preferred antistatic polyamide composition of isotropic pitch-based carbon fibers has a lower volume resistivity.
由实施例8/22/23可知，优选多臂碳纳米管与分叉状阵列碳纳米结构，更优选多臂碳纳米管。From Examples 8/22/23, it can be known that multi-armed carbon nanotubes and bifurcated array carbon nanostructures are preferred, and multi-armed carbon nanotubes are more preferred.
由实施例8/24-27可知，优选硫酸钙纤维。As can be seen from Examples 8/24-27, calcium sulfate fibers are preferred.
表4：对比例1-7抗静电聚酰胺组合物各组分含量(重量份)及测试结果Table 4: Contents (parts by weight) and test results of each component of the antistatic polyamide composition of Comparative Example 1-7
Figure PCTCN2022106378-appb-000005
Figure PCTCN2022106378-appb-000005
Figure PCTCN2022106378-appb-000006
Figure PCTCN2022106378-appb-000006
由对比例1/2可知，在本发明体系中，其他碳纤维的技术效果不好。It can be seen from Comparative Example 1/2 that in the system of the present invention, the technical effects of other carbon fibers are not good.
由对比例3可知，玻璃纤维无法替代本发明的矿物纤维。It can be seen from Comparative Example 3 that glass fiber cannot replace the mineral fiber of the present invention.
由对比例4-7可知，石墨炔、C60、纳米级炭黑、石墨烯的技术效果都不好。As can be seen from Comparative Examples 4-7, the technical effects of graphyne, C60, nano-scale carbon black, and graphene are not good.
表5：对比例8-11抗静电聚酰胺组合物各组分含量(重量份)及测试结果Table 5: Contents (parts by weight) and test results of each component of the antistatic polyamide composition of Comparative Examples 8-11
 the 对比例8Comparative example 8 对比例9Comparative example 9 对比例10Comparative example 10 对比例11Comparative example 11
PA10TPA10T 4545 4545 4545 4545
PA612PA612 1515 1515 1515 1515
各项同性沥青系碳纤维AIsotropic pitch-based carbon fiber A 11 2020 1010 1010
硫酸钙纤维ACalcium Sulfate Fiber A 2020 2020 2020 2020
单臂碳纳米管single-armed carbon nanotubes 22 22 0.010.01 66
抗氧剂antioxidant 0.30.3 0.30.3 0.30.3 0.30.3
发尘性测试(A样板)Dust generation test (A sample) 2级level 2 2级level 2 1级Level 1 3级Level 3
发尘性测试(B样板)Dust generation test (B sample) 5级Level 5 4级level 4 5级Level 5 4级level 4
体积电阻率，ohm·cmVolume resistivity, ohm cm 8.1×10 11 8.1×10 11 4.8×10 9 4.8×10 9 1.3×10 10 1.3×10 10 6.1×10 9 6.1×10 9
表面粗糙度，μmSurface roughness, μm 0.160.16 0.210.21 0.120.12 0.270.27
表6：对比例12-14抗静电聚酰胺组合物各组分含量(重量份)及测试结果Table 6: Contents (parts by weight) and test results of each component of the antistatic polyamide composition of Comparative Examples 12-14
 the 对比例12Comparative example 12 对比例13Comparative example 13 对比例14Comparative example 14
PA10TPA10T 4545 4545 4545
PA612PA612 1515 1515 1515
各项同性沥青系碳纤维AIsotropic pitch-based carbon fiber A 1010 1010 1010
硫酸镁纤维Magnesium Sulfate Fiber 2020  the  the
多晶莫来石纤维polycrystalline mullite fiber  the 2020  the
氧化铝纤维Alumina fiber  the  the 2020
单臂碳纳米管single-armed carbon nanotubes 22 22 22
抗氧剂antioxidant 0.30.3 0.30.3 0.30.3
发尘性测试(A样板)Dust generation test (A sample) 3级Level 3 4级level 4 4级level 4
发尘性测试(B样板)Dust generation test (B sample) 5级Level 5 4级level 4 5级Level 5
体积电阻率，ohm·cmVolume resistivity, ohm cm 1.6×10 11 1.6×10 11 8.4×10 9 8.4×10 9 5.3×10 10 5.3×10 10
表面粗糙度，μmSurface roughness, μm 0.270.27 0.360.36 0.410.41

Claims (10)

  1. 一种抗静电聚酰胺组合物，其特征在于，按重量份计，包括以下组分：An antistatic polyamide composition is characterized in that, by weight, it comprises the following components:
    Figure PCTCN2022106378-appb-100001
    Figure PCTCN2022106378-appb-100001
    所述的矿物纤维选自硅灰石纤维、硫酸钙纤维、硅酸钙纤维、硅酸铝纤维、海泡石纤维中的至少一种。The mineral fiber is selected from at least one of wollastonite fiber, calcium sulfate fiber, calcium silicate fiber, aluminum silicate fiber and sepiolite fiber.
  2. 根据权利要求1所述的抗静电聚酰胺组合物，其特征在于，所述的聚酰胺树脂选自半芳香聚酰胺、脂肪族聚酰胺中的至少一种；所述的半芳香聚酰胺选自PA6T/66、PA6I、PA6T/6I、PA6T/M5T、PA9T、PA9T/66、PA10T、PA10T/66、PA10T/10I、PA10T/1010、PA12T、PA12I中的至少一种；所述的脂肪族聚酰胺选自PA6、PA66、PA610、PA612、PA1010、PA1012、PA1212、PA11、PA12中的至少一种。Antistatic polyamide composition according to claim 1, is characterized in that, described polyamide resin is selected from at least one in semi-aromatic polyamide, aliphatic polyamide; Described semi-aromatic polyamide is selected from At least one of PA6T/66, PA6I, PA6T/6I, PA6T/M5T, PA9T, PA9T/66, PA10T, PA10T/66, PA10T/10I, PA10T/1010, PA12T, PA12I; the aliphatic polyamide At least one selected from PA6, PA66, PA610, PA612, PA1010, PA1012, PA1212, PA11, and PA12.
  3. 根据权利要求2所述的抗静电聚酰胺组合物，其特征在于，优选的，以聚酰胺树脂的总重量计，半芳香聚酰胺75-100wt％，脂肪族聚酰胺0-25wt％；更优选的，以聚酰胺树脂的总重量计，半芳香聚酰胺85-100wt％，脂肪族聚酰胺0-15wt％。The antistatic polyamide composition according to claim 2, is characterized in that, preferably, based on the total weight of the polyamide resin, semi-aromatic polyamide 75-100wt%, aliphatic polyamide 0-25wt%; more preferably According to the total weight of the polyamide resin, the semi-aromatic polyamide is 85-100 wt%, and the aliphatic polyamide is 0-15 wt%.
  4. 根据权利要求1所述的抗静电聚酰胺组合物，其特征在于，所述的各项同性沥青系碳纤维的平均直径为2-20微米；优选的，所述的各项同性沥青系碳纤维的平均直径为12-14微米。The antistatic polyamide composition according to claim 1, wherein the average diameter of the isotropic pitch-based carbon fibers is 2-20 microns; preferably, the average diameter of the isotropic pitch-based carbon fibers 12-14 microns in diameter.
  5. 根据权利要求1所述的抗静电聚酰胺组合物，其特征在于，所述的纳米结构碳选自单臂碳纳米管、多臂碳纳米管、分叉状阵列型碳纳米结构物中的至少一种；优选的，所述的纳米结构碳选自多臂碳纳米管。antistatic polyamide composition according to claim 1, is characterized in that, described nanostructure carbon is selected from single-arm carbon nanotube, multi-arm carbon nanotube, bifurcated array type carbon nanostructure at least One; Preferably, the nanostructured carbon is selected from multi-armed carbon nanotubes.
  6. 根据权利要求1或5所述的抗静电聚酰胺组合物，其特征在于，所述的纳米结构碳的纳米维度尺寸为0.5～50纳米。The antistatic polyamide composition according to claim 1 or 5, characterized in that the nano-dimensional size of the nanostructured carbon is 0.5-50 nanometers.
  7. 根据权利要求1所述的抗静电聚酰胺组合物，其特征在于，所述矿物纤维的平均直径是0.5-15微米；优选的，所述矿物纤维的平均直径是2-8微米；优选的，所述的矿物纤维选自硫酸钙纤维。Antistatic polyamide composition according to claim 1, is characterized in that, the average diameter of described mineral fiber is 0.5-15 micron; Preferably, the average diameter of described mineral fiber is 2-8 micron; Preferably, The mineral fibers are selected from calcium sulfate fibers.
  8. 根据权利要求1-7任一项所述的抗静电聚酰胺组合物，其特征在于，抗静电聚酰胺组合物的体积电阻率值小于等于9.9×10 8ohm·cm。 The antistatic polyamide composition according to any one of claims 1-7, characterized in that the volume resistivity of the antistatic polyamide composition is less than or equal to 9.9×10 8 ohm·cm.
  9. 根据权利要求1-8任一项所述的抗静电聚酰胺组合物的制备方法，其特征在于，按照配比将聚酰胺树脂、纳米结构碳混合均匀，再加入双螺杆挤出机主喂料口，将各项同性沥青系碳 纤维通过第一侧喂料机加入双螺杆挤出机，将矿物纤维通过第二侧喂料机加入双螺杆挤出机，熔融挤出、造粒，即得到抗静电聚酰胺组合物；其中，螺杆的转速范围是200～500rpm，长径比是40:1～48:1，温度范围是270-320℃。According to the preparation method of the antistatic polyamide composition described in any one of claims 1-8, it is characterized in that, according to the proportion, the polyamide resin and nanostructured carbon are mixed evenly, and then the main feed of the twin-screw extruder is added The isotropic pitch-based carbon fiber is fed into the twin-screw extruder through the first side feeder, and the mineral fiber is added into the twin-screw extruder through the second side feeder, melt-extruded and granulated to obtain the anti- Electrostatic polyamide composition; wherein, the rotational speed range of the screw is 200-500rpm, the aspect ratio is 40:1-48:1, and the temperature range is 270-320°C.
  10. 权利要求1-8任一项所述的抗静电聚酰胺组合物的应用，其特征在于，用于制备摄像头模组部件。The application of the antistatic polyamide composition according to any one of claims 1-8, characterized in that it is used to prepare camera module components.
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