CN113667299A - Antistatic polyamide composition and preparation method and application thereof - Google Patents

Antistatic polyamide composition and preparation method and application thereof Download PDF

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CN113667299A
CN113667299A CN202110862523.7A CN202110862523A CN113667299A CN 113667299 A CN113667299 A CN 113667299A CN 202110862523 A CN202110862523 A CN 202110862523A CN 113667299 A CN113667299 A CN 113667299A
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fiber
carbon
polyamide
antistatic
polyamide composition
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CN113667299B (en
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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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Kingfa Science and Technology Co Ltd
Zhuhai Vanteque Speciality Engineering Plastics Co Ltd
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Kingfa Science and Technology Co Ltd
Zhuhai Vanteque Speciality Engineering Plastics Co Ltd
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/02Fibres or whiskers
    • C08K7/04Fibres or whiskers inorganic
    • C08K7/06Elements
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/04Carbon
    • C08K3/041Carbon nanotubes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/02Fibres or whiskers
    • C08K7/04Fibres or whiskers inorganic
    • C08K7/08Oxygen-containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06Polyamides derived from polyamines and polycarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/002Physical properties
    • C08K2201/003Additives being defined by their diameter
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/04Antistatic

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Engineering & Computer Science (AREA)
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Abstract

The invention discloses an antistatic polyamide composition, which comprises the following components in parts by weight: 60 parts of polyamide resin; 2-18 parts of isotropic pitch carbon fiber; 10-40 parts of mineral fiber; 0.05-5 parts of nano-structured carbon; the mineral fiber is selected from at least one of wollastonite fiber, calcium sulfate fiber, calcium silicate fiber, aluminum silicate fiber and sepiolite fiber. By compounding the isotropic pitch carbon fibers, the mineral fibers and the nanostructured carbon, the defects on the surface of a workpiece can be effectively reduced, and the workpiece has good antistatic dust absorption and spontaneous dust absorption resistance.

Description

Antistatic polyamide composition and preparation method and application thereof
Technical Field
The invention relates to the technical field of high polymer materials, in particular to an antistatic polyamide composition and a preparation method and application thereof.
Background
With the development of modern technology, imaging systems are rapidly popularized in daily life, and the key of the imaging systems is various lenses, such as mobile phone camera module lenses, notebook computer/AIO all-in-one lenses, monitoring lenses, vehicle-mounted lenses, scanner lenses, multimedia television built-in camera lenses, and the like. The existing lens is modularized and called as a camera module, and mainly comprises a lens, a voice coil motor, a photosensitive chip, a sensor, an infrared filter, a circuit board and other components.
As an important component of the camera module, the plastic lens holder needs to have the following characteristics: heat resistance, adhesiveness, dimensional stability, moldability, low dust generation property, and surface smoothness.
In the using process, the definition of the imaging effect of the camera is continuously reduced along with the prolonging of the using time, the main reason is that the lens is polluted by granular dust (the size is larger than 10 μm), the granular dust mainly comes from two aspects, one is external dust caused by the untight module packaging, the dust pollution is greatly related to the electrostatic dust collection effect of an insulating plastic material in the module, the other important source is granules (the main component is a filler in the plastic lens support) falling out when the plastic lens support is vibrated or rubbed in transmission, and therefore, as a lens support material, the lens support material should have the characteristics of antistatic dust collection as high as possible and low spontaneous dust generation so as to keep the lens clean for a long time.
Regarding the surface smoothness, on the one hand, the plastic material lens holder plays a role not only in supporting the lens but also in driving support during the lens extension and retraction, and the surface smoothness of the material has an important influence on the lubricating and wear-resistant characteristics during the driving movement, and therefore, the material is required to have high surface smoothness in order to obtain excellent lubricating and wear-resistant properties. On the other hand, parts with uneven surfaces are prone to falling off of fine particles during long-term use. Therefore, the surface smoothness is also strongly associated with low dust generation properties.
Among them, heat resistance, adhesiveness, dimensional stability, and moldability are satisfied by preference of the matrix resin or other means, and high surface smoothness can be surface-adjusted by the plastic filler. However, achieving both high surface smoothness and low dusting remains an industry challenge, involving the self-dusting and electrostatic dusting properties of the material.
Disclosure of Invention
The present invention has been made to overcome the above-mentioned technical drawbacks and an object of the present invention is to provide an antistatic polyamide composition having the advantages of surface smoothness, antistatic dust-absorbing properties and anti-dusting properties.
Another object of the present invention is to provide a process for the preparation and use of the above antistatic polyamide composition.
The invention is realized by the following technical scheme:
an antistatic polyamide composition comprises the following components in parts by weight:
60 parts of polyamide resin;
2-18 parts of isotropic pitch carbon fiber;
10-40 parts of mineral fiber;
0.05-5 parts of nano-structured carbon;
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 at least one of PA6T/66, PA6I, PA6T/6I, PA6T/M5T, PA9T, PA9T/66, PA10T, PA10T/66, PA10T/10I, PA10T/1010, PA12T and PA 12I; the aliphatic polyamide is selected from at least one of PA6, PA66, PA610, PA612, PA1010, PA1012, PA1212, PA11 and PA 12.
The weight average molecular weight of the polyamide resin of the present invention is not particularly limited, and generally the object of the present invention can be achieved within the range of 5000-.
The polyamide resin of the present invention may be selected from pure aliphatic polyamide, pure semi-aromatic polyamide, and a combination of aliphatic polyamide and semi-aromatic polyamide resins. When the combination of aliphatic polyamide and semi-aromatic polyamide resin or pure semi-aromatic polyamide is selected, preferably, the semi-aromatic polyamide accounts for 75-100wt% and the aliphatic polyamide accounts for 0-25wt% of the total weight of the polyamide resin; more preferably, the semi-aromatic polyamide is 85 to 100wt% and the aliphatic polyamide is 0 to 15wt%, based on the total weight of the polyamide resin.
The average diameter of the isotropic pitch carbon fiber is 2-20 microns; preferably, the isotropic pitch-based carbon fiber has an average diameter of 12 to 14 μm.
The nano-structure carbon is selected from at least one of single-arm carbon nano-tubes, multi-arm carbon nano-tubes and forked array type carbon nano-structures; preferably, the nanostructured carbon is selected from multi-arm carbon nanotubes. The preferred nanostructured carbon forms a more extensive percolating structure network, while the antistatic polyamide composition articles have better surface smoothness and are less prone to self-abrasive dust generation over long periods of time.
In the prior art, the nano conductive carbon material includes graphene, C60, nano carbon black, and the like, in addition to the nano structured carbon. However, in the system of the present invention, the nano conductive carbon material has a poor dispersibility as compared with the nano structured carbon, and thus the surface smoothness of the product is lowered, and self-abrasion dust is generated after a long time use.
Preferably, the nano-dimension of the nano-structure carbon is 0.5-50 nm.
The nano-dimension means: the dimension range of the nano object reaching the nano dimension in 3 dimensions (for an object, the shape and the size of the material can be defined through 3 spatial dimensions, for a nano-scale material, the nano concept does not need 3 dimensions to reach the nano scale, and the nano material can be called as the nano material only by reaching the nano scale by one dimension). Such as average diameter, average thickness, length, average length, particle size, average particle size, and the like.
The mineral fibers have an average diameter of 0.5 to 15 microns; preferably, the mineral fibers have an average diameter of 2 to 8 microns; preferably, the mineral fibers are selected from calcium sulfate fibers.
The antistatic polyamide composition of the invention has a volume resistivity value of 9.9X 10 or less8ohm·cm。
0-2 parts of antioxidant and ultraviolet resistant agent can be added according to actual requirements to improve the oxidation resistance, ultraviolet resistance and the like.
The antioxidant can be antioxidant 1010, etc., and the skilled person can select the type of antioxidant to add according to actual conditions.
According to the preparation method of the antistatic polyamide composition, the polyamide resin and the nano-structure carbon are uniformly mixed according to the proportion, then the mixture is added into a main feeding port of a double-screw extruder, various isotropic pitch carbon fibers are added into the double-screw extruder through a first side feeding machine, mineral fibers are added into the double-screw extruder through a second side feeding machine, and the mixture is subjected to melt extrusion and granulation to obtain the antistatic polyamide composition; wherein the rotation speed range of the screw is 200-500 rpm, the length-diameter ratio is 40: 1-48: 1, and the temperature range is 270-320 ℃.
The antistatic polyamide composition is applied to preparing camera module components.
Compared with the prior art, the invention has the following beneficial effects
In order to realize good antistatic performance, the prior art mainly forms a percolation structure network required by antistatic by compounding carbon fiber with a certain content and nano-structure carbon (or other nano conductive carbon materials). However, if the carbon fiber content is too high, it may cause floating defects due to its large microscopic size and extremely excellent heat transfer characteristics; if the content of the nano-structure carbon (or other nano conductive carbon materials) is too high, the surface of a workpiece is not smooth due to excessive gas inclusion and agglomeration inside the nano-structure carbon (or other nano conductive carbon materials), self-dust is easily generated, and a percolation structure network is also damaged.
In order to solve the technical defects, the viscosity of the system is improved by adding the mineral fiber, so that the shearing action of a screw on the melt of the composition is effectively transmitted during extrusion processing, and the dispersion/distribution condition of fillers (isotropic pitch carbon fiber, nano-structure carbon and mineral fiber) is obviously improved. Not only can the isotropic pitch carbon fiber and the nanostructured carbon form a good percolation structure network under low content, but also can the damage to the surface smoothness under high content of the isotropic pitch carbon fiber and the nanostructured carbon.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
The raw materials used in the invention are as follows:
PA 6T/66: vicyl 4X, Kingo science and technology, Inc., weight average molecular weight 30000 g/mol;
PA 10T: vicyl 7X, Kingo science Inc., weight average molecular weight 10000 g/mol;
PA 10T/1010: vicyl 8X, King Kogyo Co., Ltd., weight average molecular weight 7000 g/mol;
PA 66: PA66 EPR24, Marasma group, China, weight average molecular weight 20000 g/mol;
PA 612: zytel 153HSL NC010, DuPont, USA, weight average molecular weight 100000 g/mol;
PA 12: grilamid L20 HL, EMS Switzerland, weight average molecular weight 70000 g/mol;
calcium sulfate fiber A: DL-40H, average diameter 2 μm, New Youwei, Changzhou;
calcium sulfate fiber B: DL-30, average diameter 4 μm, New Material Inc., Guangwei, Changzhou;
calcium sulfate fiber C: DL-10, average diameter 8 μm, New Material Inc., Guangwei, Changzhou;
calcium sulfate fiber D: NP-M01, average diameter 0.7 μ M, Jiangxi Pelargonium new Material science and technology Co., Ltd;
calcium sulfate fiber E: calcium sulfate whisker with average diameter of 14 μm, new material of Jade element of Jinan, Inc.
Wollastonite fiber: acicular wollastonite having an average diameter of 10 μm, Jiangxi Hua Jie Tai mineral fibre science and technology Co., Ltd;
calcium silicate fiber: MD1250-10012, average diameter 7 μm, shanghai hua zhong trade ltd;
aluminum silicate fiber: aluminum silicate powder with a diameter of 7 μm, Shandong Ming Ye refractory fiber Co., Ltd;
sepiolite fibers: sepiolite fibers, 15 μm in diameter, Shijiazhuanhui mineral products, Inc.;
glass fiber: EC11-3.0, round chopped glass fiber, average diameter 10 μm, taiwan obligatory corporation;
magnesium sulfate fiber: NP-YW2, average diameter 4 μm, Shanghai Pelargonium composite New Material science and technology Co., Ltd;
polycrystalline mullite fiber: t-1600, average diameter 4 μm, Kazuki Kanji Crystal fiber Limited;
alumina fiber: t-1700, average diameter 4 μm, Kaaware Crystal fiber, Zhejiang;
isotropic pitch-based carbon fiber a: DONAARBO S-242, average diameter 13 μm, Osaka gas Chemicals, Japan;
isotropic pitch-based carbon fiber B: DONAARBO S-344, average diameter 18 μm, Osaka gas Chemicals, Japan;
anisotropic pitch-based carbon fiber: XN80, average diameter 11 μm, Japan graphite fibers;
PAN-based carbon fiber: PX35CA0250-65, average diameter 7 μm, Toray Japan;
single-arm carbon nanotubes: TUBALL single-walled carbon nanotubes, average diameter 2.0nm, Oakhicle trade (Shenzhen) Limited;
multi-arm carbon nanotubes: NANOCYL NC7000, average diameter 9.5nm, NANOCYL, Belgium;
bifurcated arrayed carbon nanostructures: CNS, average nanometer dimension 5.0nm, cabot corporation;
graphite alkyne: average thickness 3nm, department of Chinese academy of sciences;
c60: fullerene C60, average particle size 0.71nm, Haohnhong biological medicine science and technology Limited;
nano-scale carbon black: nano carbon black, average particle size 15nm, cabot corporation;
graphene: high-conductivity graphene powder with a flaky shape and a lamella thickness of 0.5nm, Deyang alkene carbon technology, Inc.;
antioxidant: antioxidant 1010, basf corporation.
Examples and comparative examples preparation of antistatic polyamide compositions: uniformly mixing polyamide resin and nano-structure carbon according to a ratio, adding the mixture into a main feeding port of a double-screw extruder, adding the isotropic pitch carbon fiber into the double-screw extruder through a first side feeding machine, adding the mineral fiber into the double-screw extruder through a second side feeding machine, and carrying out melt extrusion and granulation to obtain the antistatic polyamide composition; wherein the rotation speed range of the screw is 300-400rpm, the length-diameter ratio is 48:1, and the temperature range is 270-320 ℃.
The test method comprises the following steps:
(1) testing the dust generation property: the samples were injection molded into 40mm x 1.0mm plaques A, B, the plaques test scenarios are as follows: (1) immediately performing dust generation test within 2h after injection molding, wherein the sample is called an A sample plate; (2) the dust development test (characterization of the antistatic dust absorption of the material) was carried out after 168h of exposure to a daily house (temperature 23 ℃, humidity 67%), this sample being referred to as B-panel. Placing the sample plate in 500mL of deionized water held by a beaker, placing the beaker with the sample in an ultrasonic cleaning machine, washing (ultrasonic frequency 40kHz, time A plate for 20 minutes and time B plate for 2 minutes), taking out the deionized water with the sample plate cleaned, placing the deionized water in a liquid pool, testing for 5 minutes at 23 ℃ by using a liquid particle counter, counting the amount Fa of dust with the diameter of more than 10 mu m by using a software program, and taking the amount Fa as a characteristic parameter of the dust generation property of the material, wherein the dust generation property rating is defined as follows: fa < 5 for level 1 (excellent), Fa < 20 for level 2 (excellent), Fa < 20 for level 3 (good), Fa < 35 for level 3 (good), Fa < 50 for level 4 (middle), and Fa < 50 for level 5 (poor). The liquid particle counter is RION KS-42BF, and the ultrasonic cleaning machine is BK-240J. Wherein, grade 1-3 is qualified, and grade 1 and grade 2 belong to low self-dust-generation level.
(2) Volume resistivity: the measurement was made with reference to IEC 60093-.
(3) Surface roughness: the surface roughness of an injection molding sample plate of 40mm multiplied by 1.0mm is tested by referring to GB/T1031-.
Table 1: EXAMPLES 1-11 antistatic Polyamide compositions content of Components (parts by weight) and test results
Example 1 Example 2 Example 3 Example 4 Example 5
PA6T/66 60
PA10T 60
PA10T/1010 60
PA66 60
PA612 60
PA12
Isotropic pitch carbon fiber A 10 10 10 10 10
Calcium sulfate fiber A 20 20 20 20 20
Single-arm carbon nanotube 2 2 2 2 2
Antioxidant agent 0.3 0.3 0.3 0.3 0.3
Dust test (A templet) Level 1 Level 1 Level 1 Stage 2 Stage 2
Dust test (B sample) Level 1 Level 1 Level 1 Level 1 Level 1
Volume resistivity, ohmcm 5.3×106 8.8×106 7.0×106 9.2×106 8.7×106
Surface roughness, μm 0.10 0.11 0.09 0.18 0.19
From examples 1 to 11, it is understood that when a combination of an aliphatic polyamide and a semi-aromatic polyamide resin is used, the dust generation suppressing property (self-dust generation, electrostatic dust collection) is better and the surface smoothness is high (roughness is low) in the preferable semi-aromatic/aliphatic ratio. In particular, the surface roughness of purely aliphatic polyamide compositions is high, which leads to a somewhat poorer self-dusting resistance.
Continuing with Table 1:
example 6 Example 7 Example 8 Example 9 Example 10 Example 11
PA6T/66 45
PA10T 59 51 45 39
PA10T/1010 45
PA66 15
PA612 1 9 15 21
PA12 15
Isotropic pitch carbon fiber A 10 10 10 10 10 10
Calcium sulfate fiber A 20 20 20 20 20 20
Single-arm carbon nanotube 2 2 2 2 2 2
Antioxidant agent 0.3 0.3 0.3 0.3 0.3 0.3
Dust test (A templet) Level 1 Level 1 Level 1 Level 1 Level 1 Level 1
Dust test (B sample) Level 1 Stage 2 Stage 2 Grade 3 Stage 2 Stage 2
Volume resistivity, ohmcm 1.6×107 4.2×107 6.6×107 5.1×108 3.8×107 5.0×107
Surface roughness, μm 0.10 0.11 0.13 0.14 0.13 0.15
Table 2: EXAMPLES 12-20 antistatic Polyamide compositions content by weight parts and test results
Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Example 19 Example 20
PA10T 45 45 45 45 45 45 45 45 45
PA612 15 15 15 15 15 15 15 15 15
Isotropic pitch carbon fiber A 10 10 10 10 2 2 14 18 18
Calcium sulfate fiber A 10 10 25 30 40
Calcium sulfate fiber B 20
Calcium sulfate fiber C 20
Calcium sulfate fiber D 20
Calcium sulfate fiber E 20
Single-arm carbon nanotube 2 2 2 2 0.05 0.8 3 5 5
Antioxidant agent 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3
Dust test (A templet) Level 1 Level 1 Level 1 Stage 2 Level 1 Level 1 Level 1 Stage 2 Stage 2
Dust test (B sample) Stage 2 Stage 2 Stage 2 Stage 2 Grade 3 Grade 3 Stage 2 Stage 2 Level 1
Volume resistivity, ohmcm 4.6×107 7.1×107 9.7×107 0.6×108 7.6×108 4.7×108 7.7×107 3.0×107 8.1×106
Surface roughness, μm 0.13 0.14 0.09 0.17 0.12 0.13 0.15 0.18 0.20
From examples 8/12-15, it is preferred that the mineral fibers have an average diameter in the range of 2-8 microns.
From examples 8/16 to 20, it is understood that as the content of the isotropic pitch-based carbon fiber and the one-armed carbon nanotube increases, the volume resistivity decreases, but the surface roughness increases, resulting in an increase in the self-dusting property.
Table 3: EXAMPLES 21-28 antistatic Polyamide compositions the content of each component (parts by weight) and the test results
Example 21 Example 22 Example 23 Example 24 Example 25 Example 26 Example 27 Example 28
PA10T 45 45 45 45 45 45 45 45
PA612 15 15 15 15 15 15 15 15
Isotropic pitch carbon fiber A 10 10 10 10 10 10 10
Isotropic pitch carbon fiber B 10
Calcium sulfate fiber A 20 20 20 20
Wollastonite fiber 20
Calcium silicate fibres 20
Aluminium silicate fibre 20
Sepiolite fiber 20
Single-arm carbon nanotube 2 2 2 2 2
Multi-arm carbon nanotube 2 2
Bifurcated array carbon nanostructures 2
Antioxidant agent 0.3 0.3 0.3 0.3 0.3 0.3 0.3
Dust test (A templet) Stage 2 Level 1 Level 1 Stage 2 Level 1 Stage 2 Stage 2 Level 1
Dust test (B sample) Stage 2 Level 1 Stage 2 Stage 2 Stage 2 Stage 2 Grade 3 Level 1
Volume resistivity, ohmcm 1.7×108 9.7×106 4.6×107 1.8×108 0.9×108 8.9×107 2.2×108 9.8×106
Surface roughness, μm 0.16 0.13 0.11 0.18 0.12 0.18 0.20 0.13
From example 8/21, it is found that the volume resistivity of the preferred antistatic polyamide composition of isotropic pitch-based carbon fibers is lower.
In example 8/22/23, multi-arm carbon nanotubes and carbon nanostructures with a bifurcated array are preferred, and multi-arm carbon nanotubes are more preferred.
From examples 8/24-27, calcium sulfate fibers are preferred.
Table 4: comparative examples 1 to 7 antistatic Polyamide compositions content of Components (parts by weight) and test results
Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6 Comparative example 7
PA10T 45 45 45 45 45 45 45
PA612 15 15 15 15 15 15 15
Isotropic pitch carbon fiber A 10 10 10 10 10
Anisotropic pitch-based carbon fiber 10
PAN-based carbon fiber 10
Calcium sulfate fiber A 20 20 20 20 20 20
Glass fiber 20
Single-arm carbon nanotube 2 2 2
Graphtylene 2
C60 2
Nano-scale carbon black 2
Graphene 2
Antioxidant agent 0.3 0.3 0.3 0.3 0.3 0.3 0.3
Dust test(A template) Stage 2 4 stage Grade 5 Grade 3 4 stage Grade 3 4 stage
Dust test (B sample) 4 stage 4 stage Grade 5 Grade 5 4 stage Grade 5 Grade 5
Volume resistivity, ohmcm 1.5×109 2.3×109 5.0×1010 2.2×1010 9.4×109 6.5×1010 8.1×1011
Surface roughness, μm 0.25 0.41 0.57 0.33 0.38 0.34 0.39
From comparative example 1/2, it can be seen that other carbon fibers are not as effective in the system of the present invention.
As can be seen from comparative example 3, the glass fiber cannot replace the mineral fiber of the present invention.
From comparative examples 4 to 7, it is clear that the technical effects of graphdiyne, C60, nano-sized carbon black and graphene are not good.
Table 5: comparative examples 8 to 11 antistatic Polyamide compositions content by weight and test results
Comparative example 8 Comparative example 9 Comparative example 10 Comparative example 11
PA10T 45 45 45 45
PA612 15 15 15 15
Isotropic pitch carbon fiber A 1 20 10 10
Calcium sulfate fiber A 20 20 20 20
Single-arm carbon nanotube 2 2 0.01 6
Antioxidant agent 0.3 0.3 0.3 0.3
Dust test (A templet) Stage 2 Stage 2 Level 1 Grade 3
Dust test (B sample) Grade 5 4 stage Grade 5 4 stage
Volume resistivity, ohmcm 8.1×1011 4.8×109 1.3×1010 6.1×109
Surface roughness, μm 0.16 0.21 0.12 0.27
Table 6: comparative examples 12 to 14 antistatic Polyamide compositions content by weight and test results
Comparative example 12 Comparative example 13 Comparative example 14
PA10T 45 45 45
PA612 15 15 15
Isotropic pitch carbon fiber A 10 10 10
Magnesium sulfate fiber 20
Polycrystalline mullite fiber 20
Alumina fiber 20
Single-arm carbon nanotube 2 2 2
Antioxidant agent 0.3 0.3 0.3
Dust test (A)Templet) Grade 3 4 stage 4 stage
Dust test (B sample) Grade 5 4 stage Grade 5
Volume resistivity, ohmcm 1.6×1011 8.4×109 5.3×1010
Surface roughness, μm 0.27 0.36 0.41

Claims (10)

1. An antistatic polyamide composition is characterized by comprising the following components in parts by weight:
60 parts of polyamide resin;
2-18 parts of isotropic pitch carbon fiber;
10-40 parts of mineral fiber;
0.05-5 parts of nano-structured carbon;
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. The antistatic polyamide composition according to claim 1, wherein the polyamide resin is at least one selected from the group consisting of semi-aromatic polyamide and aliphatic polyamide; the 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 and PA 12I; the aliphatic polyamide is selected from at least one of PA6, PA66, PA610, PA612, PA1010, PA1012, PA1212, PA11 and PA 12.
3. Antistatic polyamide composition according to claim 2, characterized in that preferably, based on the total weight of the polyamide resin, the semi-aromatic polyamide ranges from 75 to 100% by weight, the aliphatic polyamide ranges from 0 to 25% by weight; more preferably, the semi-aromatic polyamide is 85 to 100wt% and the aliphatic polyamide is 0 to 15wt%, based on the total weight of the polyamide resin.
4. Antistatic polyamide composition according to claim 1, characterized in that the isotropic pitch carbon fibers have an average diameter of 2-20 μm; preferably, the isotropic pitch-based carbon fiber has an average diameter of 12 to 14 μm.
5. The antistatic polyamide composition of claim 1 wherein the nanostructured carbon is selected from at least one of single-arm carbon nanotubes, multi-arm carbon nanotubes, and carbon nanostructures in a bifurcated array; preferably, the nanostructured carbon is selected from multi-arm carbon nanotubes.
6. The antistatic polyamide composition of claim 1 or 5 wherein the nano-structured carbon has a nano-dimensional size of 0.5 to 50 nm.
7. Antistatic polyamide composition according to claim 1, characterized in that the mineral fibers have an average diameter of 0.5-15 μm; preferably, the mineral fibers have an average diameter of 2 to 8 microns; preferably, the mineral fibers are selected from calcium sulfate fibers.
8. Antistatic polyamide composition according to any one of claims 1 to 7, characterized in that the antistatic polyamide composition has a volume resistivity value of 9.9 x 10 or less8ohm·cm。
9. The preparation method of the antistatic polyamide composition according to any one of claims 1 to 8, characterized in that the polyamide resin and the nanostructured carbon are uniformly mixed according to the proportion, then the mixture is added into a main feeding port of a double-screw extruder, the isotropic pitch carbon fiber is added into the double-screw extruder through a first side feeding machine, the mineral fiber is added into the double-screw extruder through a second side feeding machine, and the mixture is subjected to melt extrusion and granulation to obtain the antistatic polyamide composition; wherein the rotation speed range of the screw is 200-500 rpm, the length-diameter ratio is 40: 1-48: 1, and the temperature range is 270-320 ℃.
10. Use of the antistatic polyamide composition according to any one of claims 1 to 8 for the production of camera module parts.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114276679A (en) * 2022-01-14 2022-04-05 昆山聚威工程塑料有限公司 Antistatic transparent nylon material and preparation method thereof
CN114561098A (en) * 2022-03-09 2022-05-31 珠海万通特种工程塑料有限公司 Semi-aromatic polyamide composite material and preparation method and application thereof
WO2023005726A1 (en) * 2021-07-29 2023-02-02 金发科技股份有限公司 Antistatic polyamide composition, preparation method therefor, and use thereof

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006213798A (en) * 2005-02-02 2006-08-17 Mitsubishi Chemicals Corp Electroconductive polyamide resin composition
CN1934303A (en) * 2004-03-22 2007-03-21 株式会社吴羽 Spun isotropic pitch-based carbon fiber yarn, composite yarn and woven fabric made by using the same, and processes for the production of them
JP2008179753A (en) * 2006-12-26 2008-08-07 Kuraray Co Ltd Polyamide resin composition and molded article comprising the same
WO2010024462A1 (en) * 2008-09-01 2010-03-04 帝人株式会社 Pitch-derived graphitized short fiber and molded object obtained using same
CN102532869A (en) * 2012-02-17 2012-07-04 南京聚隆科技股份有限公司 Heat-conducting antistatic carbon fiber modified polyamide composite material and preparation method thereof
JP2016150992A (en) * 2015-02-18 2016-08-22 ユニチカ株式会社 Polyamide resin composition
JP2017210591A (en) * 2016-05-27 2017-11-30 三菱エンジニアリングプラスチックス株式会社 Polyamide resin composition, molded article, and method for producing polyamide resin composition
CN108752919A (en) * 2018-07-10 2018-11-06 芜湖市元奎新材料科技有限公司 Heat conduction fire retardation wear-resistance nylon composite material and preparation method thereof

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101374361B1 (en) * 2010-08-20 2014-03-18 제일모직주식회사 Bracket for protecting lcd of portable display device
WO2012161064A1 (en) * 2011-05-20 2012-11-29 東洋紡株式会社 Polyamide resin composition for optical components
EP2930212B1 (en) * 2014-04-08 2019-04-10 Ems-Patent Ag Electrically conductive polyamide moulding compositions
CN108929540A (en) * 2018-06-27 2018-12-04 合肥卓创新材料有限公司 A kind of halogen-free flame-proof antistatic polyamide material and its preparation process
CN113667299B (en) * 2021-07-29 2023-04-11 金发科技股份有限公司 Antistatic polyamide composition and preparation method and application thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1934303A (en) * 2004-03-22 2007-03-21 株式会社吴羽 Spun isotropic pitch-based carbon fiber yarn, composite yarn and woven fabric made by using the same, and processes for the production of them
JP2006213798A (en) * 2005-02-02 2006-08-17 Mitsubishi Chemicals Corp Electroconductive polyamide resin composition
JP2008179753A (en) * 2006-12-26 2008-08-07 Kuraray Co Ltd Polyamide resin composition and molded article comprising the same
WO2010024462A1 (en) * 2008-09-01 2010-03-04 帝人株式会社 Pitch-derived graphitized short fiber and molded object obtained using same
CN102532869A (en) * 2012-02-17 2012-07-04 南京聚隆科技股份有限公司 Heat-conducting antistatic carbon fiber modified polyamide composite material and preparation method thereof
JP2016150992A (en) * 2015-02-18 2016-08-22 ユニチカ株式会社 Polyamide resin composition
JP2017210591A (en) * 2016-05-27 2017-11-30 三菱エンジニアリングプラスチックス株式会社 Polyamide resin composition, molded article, and method for producing polyamide resin composition
CN108752919A (en) * 2018-07-10 2018-11-06 芜湖市元奎新材料科技有限公司 Heat conduction fire retardation wear-resistance nylon composite material and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023005726A1 (en) * 2021-07-29 2023-02-02 金发科技股份有限公司 Antistatic polyamide composition, preparation method therefor, and use thereof
CN114276679A (en) * 2022-01-14 2022-04-05 昆山聚威工程塑料有限公司 Antistatic transparent nylon material and preparation method thereof
CN114561098A (en) * 2022-03-09 2022-05-31 珠海万通特种工程塑料有限公司 Semi-aromatic polyamide composite material and preparation method and application thereof
CN114561098B (en) * 2022-03-09 2023-08-15 珠海万通特种工程塑料有限公司 Semi-aromatic polyamide composite material and preparation method and application thereof

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