CN111286191A - High-strength, high-brightness black and glass fiber reinforced nylon material and preparation method thereof - Google Patents
High-strength, high-brightness black and glass fiber reinforced nylon material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-strength, high-brightness black and glass fiber reinforced nylon material and a preparation method thereof, wherein the material comprises the following components in percentage by mass: 35-79.5% of nylon; transparent nylon: 10-30%; glass fiber: 10-30%; functional master batch: 0.5-2%; antioxidant: 0 to 1 percent; 0-1% of a lubricant; 0-1% of scratch-resistant auxiliary agent. The invention has the beneficial effects that: according to the invention, the crystallinity of the nylon material is controlled, the material is ensured to have higher glossiness by matching with an injection molding process, and the covering of the glass fiber of the reinforced nylon material and the improvement of blackness and gloss are realized by adding the self-made functional master batch. The nylon composite material prepared by the invention meets the requirements of parts on the mechanical property of the material, can achieve the appearance effect of high brightness and black without spraying, and solves the problem that the strength and the appearance can not be considered simultaneously.
Description
Technical Field
The invention relates to application of glass fiber reinforced nylon as an appearance part, in particular to a high-strength, high-brightness black and glass fiber reinforced nylon material and a preparation method thereof.
Background
The environment-friendly and energy-saving automobile paint spraying-free product is a main trend of automobile development, is more and more popular, is a product which can achieve the beautiful appearance effect required by paint spraying without spraying and directly injection molding at one time, has the characteristics of good surface gloss, rich colors, scratch resistance, corrosion resistance, more environmental protection, capability of recycling 100 percent, lower comprehensive cost and the like, can meet the diversified aesthetic requirements, and is mature in the fields of household electricity and automobiles.
The existing spraying-free materials on the market mainly comprise ABS, PC/ABS, ASA/PMMA, PBT, PA and other materials, although the spraying-free materials are wide in variety, many problems still exist in the application and popularization of the existing spraying-free materials, the problem to be solved needs to be solved urgently, the spraying-free materials mainly adopt non-filled materials, the effect of high surface gloss is difficult to achieve for glass fiber or mineral filled materials, because the strength of the non-filled materials is low, the existing spraying-free materials are mainly applied to decorating parts with low requirements on strength, the spraying-free materials are limited by product structures, the spraying-free products usually generate appearance problems such as flow marks, welding lines and the like in the injection molding process, the application of the materials is limited, and the spraying-free materials are required to be applied from the structural design stage to obtain good appearance effects.
PA is used as engineering plastic, has high mechanical strength, excellent wear resistance and excellent chemical corrosion resistance, and is widely applied to the fields of automobiles, household appliances and the like, because nylon has the advantage of wear resistance, spraying-free nylon materials are increasingly researched as appearance parts, but the current main research is mainly focused on non-filling materials, the filling materials have higher mechanical strength, and the PA can be used in some fields with appearance and strength requirements, such as television bracket materials, and once the spraying-free technology for reinforcing the nylon materials is broken through, the PA has important significance for increasing the application of the spraying-free materials.
Disclosure of Invention
The invention provides a preparation method of a high-strength, spraying-free and high-brightness black glass fiber reinforced nylon material, through scientific design of a formula, the glass fiber reinforcement endows the nylon material with good mechanical properties, the addition of special nylon increases the glossiness of the nylon material, and the addition of functional master batches endows the nylon material with good appearance and blackness, so that the nylon material meets the highlight effect.
In order to solve the technical problems, the invention adopts the technical scheme that:
a high-strength, high-brightness black and glass fiber reinforced nylon material comprises the following raw materials in percentage by weight:
the nylon can be PA6, PA66, PA6/66 or the mixture of the above raw materials.
The glass fiber glass type is E glass, the alkali content is less than 0.8 percent, the monofilament fiber diameter is as follows: 10. + -.1 μm, bulk density 0.70. + -. 0.15g/cm3, length: 3mm, and the water content is less than or equal to 0.05 percent;
the transparent nylon can be fat continuous transparent nylon or semi-aromatic transparent nylon;
the functional master batch is high-pigment carbon black: nigrosine: carbon nanotube: the lubricant is prepared by banburying and forming according to the proportion of 4:4:1: 1.
The effective content of phenyl silicone is 50%.
The antioxidant is a 1:1 mixture of phosphite and hindered phenol.
The scratch-resistant auxiliary agent is organic clay subjected to special surface treatment.
The invention provides a preparation method of a high-strength, high-brightness black and glass fiber reinforced nylon material, which comprises the following steps:
(1) weighing the dried raw materials according to the formula proportion; uniformly mixing nylon, transparent nylon, functional master batches, an antioxidant and a lubricant by a high-speed stirrer for later use, and weighing glass fibers according to the proportion for later use;
(2) adding the nylon mixed raw materials into a double-screw extruder through a main feeding port, adding glass fibers into the double-screw extruder from a side feeding port, and performing melt extrusion, granulation, drying and other processes to obtain the nylon composite material.
Compared with the prior art, the invention has the advantages that: the invention provides a spraying-free highlight black material mainly comprising a non-filling material system in the market at present, wherein the non-filling system can obtain a good appearance effect, but has low strength, the technical barrier for achieving the highlight appearance effect of glass fiber mineral filling materials is high, the materials belong to the blank in the market at present, the invention self-prepares a functional master batch containing high-pigment carbon black, carbon nano tubes, nigrosine and a dispersing agent, the carbon nano tubes and the high-pigment carbon black have high dyeing efficiency, the material can be endowed with good blackness, the nigrosine has good dyeing effect on fillers, the material can be endowed with good appearance and gloss, the gloss effect of the material is further increased by adding transparent nylon, the matching use of a base material formula and the functional master batch in the formula meets the requirements of enhancing the high gloss and blackness of nylon materials, and the material can be used as an appearance piece without spraying, meanwhile, in order to avoid the defect that a highlight material is easy to scratch, a high-efficiency scratch-resistant auxiliary agent is introduced into a material formula, a core component functional master batch formula of the formula is independently developed, and the dispersion of the additive plays a crucial role in appearance effect, so that the additive is more favorably dispersed when the additive is added into the material formula in the form of master batch. By scientifically designing the product formula, the product has excellent appearance on the premise of ensuring that the material has high mechanical properties, so that the product can meet the use requirements of appearance parts on the premise of not spraying, and can be used as parts such as automobile parts, television supports and the like with higher requirements on appearance and strength.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention clearer, the present invention will be further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The following materials were used in the examples of the invention:
PA66 FYR27D, Congress of the Gong horse group, China;
PA6 MF800, Rimefu industries, Inc., Jiangsu;
PA6/66HYG-2500E Jiangsu Haiyang chemical fibers, Inc.;
TM01, santong chen sen new materials science and technology ltd;
TM03, santong chen sen new materials science and technology ltd;
TM041, santon corp, rey new materials science and technology ltd;
glass fiber: 301HP, diameter 10 μm, Chongqing International composite Co., Ltd
Lubricant: silicone powder, technical grade, commercially available;
antioxidant 1098: n, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine, commercially available;
antioxidant 168: tris [ 2.4-di-tert-butylphenyl ] phosphite, commercially available;
high pigment carbon black: the particle size is 9-17 nm, and the particle size is sold in the market;
carbon nanotube: single-walled carbon nanotubes, tube diameter: 1-2 nm, length: 10 to 20 μm, commercially available.
Nigrosine: is sold on the market;
lubricant: OP wax, commercially available;
functional master batches are self-made, and high-pigment carbon black is subjected to: nigrosine: carbon nanotube: the lubricant is prepared by banburying and forming according to the proportion of 4:4:1: 1;
scratch-resistant auxiliary agent: Solid-TT, TER Co
The product performance testing method comprises the following steps:
tensile property: according to ISO527 method, spline size: 170 × 10 × 4mm, test speed 5 mm/min.
Bending property: according to ISO178 method, spline size: 80 x 10 x 4mm, test speed 2 mm/min.
Notched impact strength: according to ISO 180 method, spline size: 80 x 10 x 4 mm.
Scratch resistance effect: FLTM BN 108-13, level 1 OK, level 2 NG
Gloss: according to the method and the device of VW 50190: BYK, spline requirement: a highlight board;
l value: equipment: 2500C high light board
Example 1:
weighing PA67.62kg, drying at 100 ℃ for 4h, and adding the functional master batch: 0.2kg of scratch-resistant auxiliary agent, 0.1kg of antioxidant, 109815 g of antioxidant, 16815g of antioxidant and 50g of lubricant are uniformly mixed in a high-speed mixer to obtain a resin mixture for later use;
weighing 301HP (E)2kg of glass fiber for later use.
Adding the resin mixture into a double-screw extruder (the diameter of a screw is 35mm, the length-diameter ratio is L/D (L/D) ═ 40) through a main feeding port, adding glass fibers into the double-screw extruder through a side feeding port, controlling the temperature of each section of the double-screw extruder (from a feeding port to a machine head outlet) to be 190 ℃, 210 ℃, 225 ℃, 220 ℃, 210 ℃ and 480r/min, and cooling strips by a water tank, drying by a blast drier and pelletizing by a pelletizer in sequence to obtain the modified nylon product.
The above materials were dried in a forced air drying oven at 120 ℃ for 4h and then injection molded into standard bars at an injection molding temperature of 260 ℃. The injection molded sample bars were conditioned for 24 hours in a laboratory standard environment (23 ℃, 50% RH) and tested, the results of which are shown in table 1.
Example 2:
weighing PA667.62kg, drying at 100 deg.C for 4h, functional master batch: 0.2kg of scratch-resistant auxiliary agent, 0.1kg of antioxidant, 109815 g of antioxidant, 16815g of antioxidant and 50g of lubricant are uniformly mixed in a high-speed mixer to obtain a resin mixture for later use;
weighing 301HP (E)2kg of glass fiber for later use.
Adding the resin mixture into a double-screw extruder (the diameter of a screw is 35mm, the length-diameter ratio is L/D (L/D) ═ 40) through a main feeding port, adding glass fibers into the double-screw extruder through a side feeding port, controlling the temperature of each section of the double-screw extruder (from a feeding port to a machine head outlet) to be 220 ℃, 240 ℃, 265 ℃, 250 ℃ and 480 ℃ and controlling the rotating speed of the double-screw extruder to be 480r/min, and cooling, drying and dicing the strips by a water tank and a blast drier in sequence to obtain the modified nylon product.
The above materials were dried in a forced air drying oven at 120 ℃ for 4h and then injection molded into standard bars at an injection molding temperature of 280 ℃. The injection molded sample bars were conditioned for 24 hours in a laboratory standard environment (23 ℃, 50% RH) and tested, the results of which are shown in table 1.
Example 3:
weighing PA 6/667.62 kg, drying the material for 4h at 100 ℃, and mixing the functional master batch: 0.2kg of scratch-resistant auxiliary agent, 0.1kg of antioxidant, 109815 g of antioxidant, 16815g of antioxidant and 50g of lubricant are uniformly mixed in a high-speed mixer to obtain a resin mixture for later use;
weighing 301HP (E)2kg of glass fiber for later use.
Adding the resin mixture into a double-screw extruder (the diameter of a screw is 35mm, the length-diameter ratio is L/D (L/D) ═ 40) through a main feeding port, adding glass fibers into the double-screw extruder through a side feeding port, controlling the temperature of each section of the double-screw extruder (from a feeding port to a machine head outlet) to be 190 ℃, 210 ℃, 225 ℃, 220 ℃, 210 ℃ and 480r/min, and cooling strips by a water tank, drying by a blast drier and pelletizing by a pelletizer in sequence to obtain the modified nylon product.
The above materials were dried in a forced air drying oven at 120 ℃ for 4h and then injection molded into standard bars at an injection molding temperature of 260 ℃. The injection-molded mechanical property sample strips are subjected to testing after being adjusted for 24 hours in a standard laboratory environment (23 ℃, 50% RH), and the test results are shown in Table 1.
Example 4:
weighing PA 65 kg, drying at 100 ℃ for 4h, drying TM032.62kg at 100 ℃ for 4h, and mixing the functional master batch: 0.2kg of scratch-resistant auxiliary agent, 0.1kg of antioxidant, 109815 g of antioxidant, 16815g of antioxidant and 50g of lubricant are uniformly mixed in a high-speed mixer to obtain a resin mixture for later use;
weighing 301HP (E)2kg of glass fiber for later use.
Adding the resin mixture into a double-screw extruder (the diameter of a screw is 35mm, the length-diameter ratio is L/D (L/D) ═ 40) through a main feeding port, adding glass fibers into the double-screw extruder through a side feeding port, controlling the temperature of each section of the double-screw extruder (from a feeding port to a machine head outlet) to be 190 ℃, 210 ℃, 225 ℃, 220 ℃, 210 ℃ and 480r/min, and cooling strips by a water tank, drying by a blast drier and pelletizing by a pelletizer in sequence to obtain the modified nylon product.
The above materials were dried in a forced air drying oven at 120 ℃ for 4h and then injection molded into standard bars at an injection molding temperature of 260 ℃. The injection molded sample bars were conditioned for 24 hours in a laboratory standard environment (23 ℃, 50% RH) and tested, the results of which are shown in table 1.
Example 5:
weighing PA 65 kg, drying at 100 ℃ for 4h, TM0412.62kg, drying at 100 ℃ for 4h, and mixing the functional master batch: 0.2kg of scratch-resistant auxiliary agent, 0.1kg of antioxidant, 109815 g of antioxidant, 16815g of antioxidant and 50g of lubricant are uniformly mixed in a high-speed mixer to obtain a resin mixture for later use;
weighing 301HP (E)2kg of glass fiber for later use.
Adding the resin mixture into a double-screw extruder (the diameter of a screw is 35mm, the length-diameter ratio is L/D (L/D) ═ 40) through a main feeding port, adding glass fibers into the double-screw extruder through a side feeding port, controlling the temperature of each section of the double-screw extruder (from a feeding port to a machine head outlet) to be 190 ℃, 210 ℃, 225 ℃, 220 ℃, 210 ℃ and 480r/min, and cooling strips by a water tank, drying by a blast drier and pelletizing by a pelletizer in sequence to obtain the modified nylon product.
The above materials were dried in a forced air drying oven at 120 ℃ for 4h and then injection molded into standard bars at an injection molding temperature of 260 ℃. The injection-molded mechanical property sample strips are subjected to testing after being adjusted for 24 hours in a standard laboratory environment (23 ℃, 50% RH), and the test results are shown in Table 1.
Example 6:
weighing PA 65 kg, drying at 100 ℃ for 4h, TM012.62kg, drying at 100 ℃ for 4h, and mixing the functional master batch: 0.2kg of scratch-resistant auxiliary agent, 0.1kg of antioxidant, 109815 g of antioxidant, 16815g of antioxidant and 50g of lubricant are uniformly mixed in a high-speed mixer to obtain a resin mixture for later use;
weighing 301HP (E)2kg of glass fiber for later use.
Adding the resin mixture into a double-screw extruder (the diameter of a screw is 35mm, the length-diameter ratio is L/D (L/D) ═ 40) through a main feeding port, adding glass fibers into the double-screw extruder through a side feeding port, controlling the temperature of each section of the double-screw extruder (from a feeding port to a machine head outlet) to be 190 ℃, 210 ℃, 225 ℃, 220 ℃, 210 ℃ and 480r/min, and cooling strips by a water tank, drying by a blast drier and pelletizing by a pelletizer in sequence to obtain the modified nylon product.
The above materials were dried in a forced air drying oven at 120 ℃ for 4h and then injection molded into standard bars at an injection molding temperature of 260 ℃. The injection-molded mechanical property sample strips are subjected to testing after being adjusted for 24 hours in a standard laboratory environment (23 ℃, 50% RH), and the test results are shown in Table 1.
Comparative example 1:
weighing PA67.62kg, drying the material at 100 ℃ for 4h, and mixing the carbon black master batch: 0.2kg of scratch-resistant auxiliary agent, 0.1kg of antioxidant, 109815 g of antioxidant, 16815g of antioxidant and 50g of lubricant are uniformly mixed in a high-speed mixer to obtain a resin mixture for later use;
weighing 301HP (E)2kg of glass fiber for later use.
Adding the resin mixture into a double-screw extruder (the diameter of a screw is 35mm, the length-diameter ratio is L/D (L/D) ═ 40) through a main feeding port, adding glass fibers into the double-screw extruder through a side feeding port, controlling the temperature of each section of the double-screw extruder (from a feeding port to a machine head outlet) to be 190 ℃, 210 ℃, 225 ℃, 220 ℃, 210 ℃ and 480r/min, and cooling strips by a water tank, drying by a blast drier and pelletizing by a pelletizer in sequence to obtain the modified nylon product.
The above materials were dried in a forced air drying oven at 120 ℃ for 4h and then injection molded into standard bars at an injection molding temperature of 260 ℃. The injection molded sample bars were conditioned for 24 hours in a laboratory standard environment (23 ℃, 50% RH) and tested, the results of which are shown in table 1.
Comparative example 2:
weighing PA667.62kg, drying at 100 deg.C for 4h, carbon black master batch: 0.2kg of scratch-resistant auxiliary agent, 0.1kg of antioxidant, 109815 g of antioxidant, 16815g of antioxidant and 50g of lubricant are uniformly mixed in a high-speed mixer to obtain a resin mixture for later use;
weighing 301HP (E)2kg of glass fiber for later use.
Adding the resin mixture into a double-screw extruder (the diameter of a screw is 35mm, the length-diameter ratio is L/D (L/D) ═ 40) through a main feeding port, adding glass fibers into the double-screw extruder through a side feeding port, controlling the temperature of each section of the double-screw extruder (from a feeding port to a machine head outlet) to be 220 ℃, 240 ℃, 265 ℃, 250 ℃ and 480 ℃ and controlling the rotating speed of the double-screw extruder to be 480r/min, and cooling, drying and dicing the strips by a water tank and a blast drier in sequence to obtain the modified nylon product.
The above materials were dried in a forced air drying oven at 120 ℃ for 4h and then injection molded into standard bars at an injection molding temperature of 280 ℃. The injection molded sample bars were conditioned for 24 hours in a laboratory standard environment (23 ℃, 50% RH) and tested, the results of which are shown in table 1.
Comparative example 3:
weighing PA 6/667.62 kg, drying at 100 ℃ for 4h, and mixing carbon black master batch: 0.2kg of scratch-resistant auxiliary agent, 0.1kg of antioxidant, 109815 g of antioxidant, 16815g of antioxidant and 50g of lubricant are uniformly mixed in a high-speed mixer to obtain a resin mixture for later use;
weighing 301HP (E)2kg of glass fiber for later use.
Adding the resin mixture into a double-screw extruder (the diameter of a screw is 35mm, the length-diameter ratio is L/D (L/D) ═ 40) through a main feeding port, adding glass fibers into the double-screw extruder through a side feeding port, controlling the temperature of each section of the double-screw extruder (from a feeding port to a machine head outlet) to be 190 ℃, 210 ℃, 225 ℃, 220 ℃, 210 ℃ and 480r/min, and cooling strips by a water tank, drying by a blast drier and pelletizing by a pelletizer in sequence to obtain the modified nylon product.
The above materials were dried in a forced air drying oven at 120 ℃ for 4h and then injection molded into standard bars at an injection molding temperature of 260 ℃. The injection-molded mechanical property sample strips are subjected to testing after being adjusted for 24 hours in a standard laboratory environment (23 ℃, 50% RH), and the test results are shown in Table 1.
Comparative example 4
Weighing PA 65 kg, drying at 100 ℃ for 4h, TM012.62kg, drying at 100 ℃ for 4h, carbon black master batch: 0.2kg of scratch-resistant auxiliary agent, 0.1kg of antioxidant, 109815 g of antioxidant, 16815g of antioxidant and 50g of lubricant are uniformly mixed in a high-speed mixer to obtain a resin mixture for later use;
weighing 301HP (E)2kg of glass fiber for later use.
Adding the resin mixture into a double-screw extruder (the diameter of a screw is 35mm, the length-diameter ratio is L/D (L/D) ═ 40) through a main feeding port, adding glass fibers into the double-screw extruder through a side feeding port, controlling the temperature of each section of the double-screw extruder (from a feeding port to a machine head outlet) to be 190 ℃, 210 ℃, 225 ℃, 220 ℃, 210 ℃ and 480r/min, and cooling strips by a water tank, drying by a blast drier and pelletizing by a pelletizer in sequence to obtain the modified nylon product.
The above materials were dried in a forced air drying oven at 120 ℃ for 4h and then injection molded into standard bars at an injection molding temperature of 260 ℃. The injection molded sample bars were conditioned for 24 hours in a laboratory standard environment (23 ℃, 50% RH) and tested, the results of which are shown in table 1.
Comparative example 5
Weighing PA67.72kg, drying at 100 ℃ for 4h, and preparing functional master batch: 0.2kg of antioxidant 109815 g, 16815g of antioxidant and 50g of lubricant are uniformly mixed in a high-speed stirrer to obtain a resin mixture for later use;
weighing 301HP (E)2kg of glass fiber for later use.
Adding the resin mixture into a double-screw extruder (the diameter of a screw is 35mm, the length-diameter ratio is L/D (L/D) ═ 40) through a main feeding port, adding glass fibers into the double-screw extruder through a side feeding port, controlling the temperature of each section of the double-screw extruder (from a feeding port to a machine head outlet) to be 190 ℃, 210 ℃, 225 ℃, 220 ℃, 210 ℃ and 480r/min, and cooling strips by a water tank, drying by a blast drier and pelletizing by a pelletizer in sequence to obtain the modified nylon product.
The above materials were dried in a forced air drying oven at 120 ℃ for 4h and then injection molded into standard bars at an injection molding temperature of 280 ℃. The injection molded sample bars were conditioned for 24 hours in a laboratory standard environment (23 ℃, 50% RH) and tested, the results of which are shown in table 1.
Table 1: and (5) performance test results.
The data shown in the table show that the addition of the functional master batch can effectively increase the L value and the gloss, the appearance is good, the appearance problems such as floating fibers and the like do not exist, the addition of the transparent nylon can effectively reduce the crystallinity of the material, increase the light transmittance of the material, increase both the gloss and the L value, the scratch-resistant auxiliary agent can effectively increase the scratch-resistant effect of the highlight material, and meet the use requirements of the highlight material, and the traditional highlight black material mainly refers to a non-filling material to realize the highlight black effect.
Claims (8)
1. The utility model provides a high strength, high bright black, glass fiber reinforced nylon material which characterized in that: the composite material comprises the following raw materials in percentage by weight:
2. the high-strength, high-brightness black and glass fiber reinforced nylon material as claimed in claim 1, wherein: the nylon can be PA6, PA66, PA6/66 or the mixture of the above raw materials.
3. The high-strength, high-brightness black and glass fiber reinforced nylon material as claimed in claim 1, wherein: the glass fiber glass type is E glass, the alkali content is less than 0.8 percent, the monofilament fiber diameter is as follows: 10. + -.1 μm, bulk density 0.70. + -. 0.15g/cm3, length: 3mm, and the water content is less than or equal to 0.05 percent.
4. The high-strength, high-brightness black and glass fiber reinforced nylon material as claimed in claim 1, wherein: the transparent nylon can be fat continuous transparent nylon or semi-aromatic transparent nylon.
5. The high-strength, high-brightness black and glass fiber reinforced nylon material as claimed in claim 1, wherein: the functional master batch is high-pigment carbon black: nigrosine: carbon nanotube: the lubricant is prepared by banburying and forming according to the proportion of 4:4:1: 1.
6. The high-strength, high-brightness black and glass fiber reinforced nylon material as claimed in claim 1, wherein: the effective content of phenyl silicone is 50%.
7. The high-strength, high-brightness black and glass fiber reinforced nylon material as claimed in claim 1, wherein: the antioxidant is a 1:1 mixture of phosphite and hindered phenol.
8. The method for preparing the high-strength, high-brightness black and glass fiber reinforced nylon material according to any one of claims 1 to 7, wherein the method comprises the following steps: the method comprises the following steps:
(1) weighing the dried raw materials according to the formula proportion; uniformly mixing nylon, transparent nylon, functional master batches, an antioxidant and a lubricant by a high-speed stirrer for later use, and weighing glass fibers according to the proportion for later use;
(2) adding the nylon mixed raw materials into a double-screw extruder through a main feeding port, adding glass fibers into the double-screw extruder from a side feeding port, and performing melt extrusion, granulation, drying and other processes to obtain the nylon composite material.
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| CN112592586A (en) * | 2020-12-14 | 2021-04-02 | 上海长伟锦磁工程塑料有限公司 | High-brightness black scratch-resistant spraying-free nylon material and preparation method thereof |
| CN112724668A (en) * | 2020-12-16 | 2021-04-30 | 金发科技股份有限公司 | Polyamide resin composition and preparation method and application thereof |
| CN112745674A (en) * | 2020-12-26 | 2021-05-04 | 广东九彩新材料有限公司 | High-pigment carbon black-polyamide color master batch and preparation method thereof |
| CN114181527A (en) * | 2021-12-22 | 2022-03-15 | 江苏特耐奇工程塑业有限公司 | Highlight PA66 glass fiber reinforced material and preparation method thereof |
| CN114773839A (en) * | 2022-03-30 | 2022-07-22 | 上海金发科技发展有限公司 | High-brightness black nylon material and preparation method and application thereof |
| CN114806154A (en) * | 2022-03-30 | 2022-07-29 | 上海金发科技发展有限公司 | High-brightness black composite nylon material and preparation method and application thereof |
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| CN114773839B (en) * | 2022-03-30 | 2023-10-13 | 上海金发科技发展有限公司 | Highlight black nylon material and preparation method and application thereof |
| CN114957982A (en) * | 2022-07-01 | 2022-08-30 | 苏州旭光聚合物有限公司 | Nylon antioxidant master batch, preparation method thereof and application thereof in high-content glass fiber reinforced nylon |
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Application publication date: 20200616 |