CN117683342A - Spraying-free high-blackness and brightness scratch-resistant PA (polyamide) alloy material as well as preparation method and application thereof - Google Patents
Spraying-free high-blackness and brightness scratch-resistant PA (polyamide) alloy material as well as preparation method and application thereof Download PDFInfo
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- CN117683342A CN117683342A CN202311729315.5A CN202311729315A CN117683342A CN 117683342 A CN117683342 A CN 117683342A CN 202311729315 A CN202311729315 A CN 202311729315A CN 117683342 A CN117683342 A CN 117683342A
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- 229920002647 polyamide Polymers 0.000 title claims description 17
- 239000000463 material Substances 0.000 claims abstract description 34
- 239000000654 additive Substances 0.000 claims abstract description 28
- 230000000996 additive effect Effects 0.000 claims abstract description 28
- 229910001125 Pa alloy Inorganic materials 0.000 claims abstract description 25
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- 229920005989 resin Polymers 0.000 claims description 34
- 239000011347 resin Substances 0.000 claims description 34
- 239000006229 carbon black Substances 0.000 claims description 24
- 239000004677 Nylon Substances 0.000 claims description 20
- 229920001778 nylon Polymers 0.000 claims description 20
- 239000012745 toughening agent Substances 0.000 claims description 16
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- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 4
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- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
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- 239000004594 Masterbatch (MB) Substances 0.000 description 2
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- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
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- SOGFHWHHBILCSX-UHFFFAOYSA-J prop-2-enoate silicon(4+) Chemical compound [Si+4].[O-]C(=O)C=C.[O-]C(=O)C=C.[O-]C(=O)C=C.[O-]C(=O)C=C SOGFHWHHBILCSX-UHFFFAOYSA-J 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a spraying-free high-blackness and high-brightness scratch-resistant PA alloy material, a preparation method and application thereof, in particular to application as an automotive interior steering wheel. At present, materials such as automobile interior instrument panels and steering wheels are painted by ABS, PC+ABS materials, the painting process is high in cost and environment-friendly, smell is large, the paint can be smeared after long-term hand touch, and the plastic ground color is leaked. The invention discloses a novel additive for preparing a spraying-free high-blackness and bright scratch-resistant PA alloy material for the first time, which unexpectedly improves the toughness of a product on the basis of effectively improving the scratch resistance and the wear resistance, and solves the problems that the existing scratch-resistant agent slightly improves the scratch resistance but reduces the toughness of the material; furthermore, the invention keeps the material qualified and resistant to grease, and solves the problem that the grease resistance of the material is reduced due to the scratch resistance in the prior art. Practical tests show that the technical scheme of the invention can meet the requirements of automotive interior materials.
Description
Technical Field
The invention belongs to polymer modification, and particularly relates to a spraying-free high-blackness and brightness scratch-resistant PA alloy material, and a preparation method and application thereof.
Background
Polyamide is commonly called Nylon (Nylon), and the English name Polyamide (PA) is a thermoplastic resin general name containing repeated amide groups (NHCO) on a molecular main chain, and comprises aliphatic PA, aliphatic-aromatic PA and aromatic PA. The materials used on the automobile are glass fiber reinforced PA6 and PA66, mainly on the framework parts with higher strength required by the automobile, but the automobile interior decoration is used for replacing the paint spraying materials, and the automobile interior decoration has the defects of insufficient blackness, poor dimensional stability and high water absorption. The key technology for preparing the highlight and highlight black scratch-resistant PA material is a transparent nylon material with low water absorption and good dimensional stability and a scratch-resistant agent. At present, materials such as automobile interior instrument panels and steering wheels are painted by ABS, PC+ABS materials, the painting process is high in cost and environment-friendly, smell is large, the paint can be smeared after long-term hand touch, and the plastic ground color is leaked.
Disclosure of Invention
The invention mainly solves the problem that the existing automotive interior is characterized by paint spraying, can obtain the Gao Guangni dragon material with no spraying, high brightness and black and scratch resistance through one-step injection molding, and can be used as an automotive interior steering wheel.
The invention adopts the following technical scheme:
a spray-free high-blackness and bright scratch-resistant PA alloy material comprises transparent nylon resin, SAN resin, a compatilizer, an additive, a toughening agent, an auxiliary agent and carbon black; preferably, the spray-free high-blackness and high-brightness scratch-resistant PA alloy material consists of transparent nylon resin, SAN resin, a compatilizer, an additive, a toughening agent, an auxiliary agent and carbon black.
The invention discloses a preparation method of a spraying-free high-blackness and high-brightness scratch-resistant PA alloy material, which comprises the following steps of melt mixing transparent nylon resin, SAN resin, a compatilizer, an additive, a toughening agent, an auxiliary agent and carbon black to obtain the spraying-free high-blackness and high-brightness and high-scratch-resistant PA alloy material. The preparation method of the spraying-free high-blackness and bright scratch-resistant PA alloy material comprises the steps of mixing raw materials, directly extruding and melting the raw materials into a double screw, respectively adding single materials into an extruder through a weight-loss type metering scale, and mixing an auxiliary agent, carbon black and the like together through a single weight-loss type metering scale.
In the invention, the mass sum of transparent nylon resin, SAN resin, compatilizer, additive, flexibilizer, auxiliary agent and carbon black is 100%, wherein:
65-85% of transparent nylon resin
SAN resin 5-25%
1-5% of compatilizer
Additive 2-7%
5 to 10 percent of toughening agent
1 to 2 percent of other processing aids
Carbon black balance
Preferably:
70-80% of transparent nylon resin
SAN resin 5-15%
5-8% of compatilizer
Additive 2-3%
6 to 7 percent of toughening agent
1 to 2 percent of other processing aids
Carbon black balance
In the invention, the transparent nylon resin is long-chain copolymerized nylon, and the transparency is more than 88 and the saturated water absorption is less than 0.5 percent.
In the invention, the melt index of the SAN resin is 10-55g/10min,220 ℃ and 10kg; the mass content of AN is 25-35%. Preferably, NF2200 (AN content 26%): melt index 30g/10min (220 ℃ C. +10 kg); NX3400 (AN content 34%): melt index 12g/10min (220 ℃ C. +10 kg); NX3260 (AN content 31%): melt index 55g/10min (220 ℃ C.+10 kg).
In the invention, the compatilizer is a styrene-maleic anhydride-acrylonitrile terpolymer; the toughening agent is a maleic anhydride grafted ethylene propylene diene monomer copolymer; the auxiliary agent is the conventional component of the existing plastic alloy, such as the combination of the common antioxidant, the ultraviolet resistance agent and the like. The carbon black is carrier-free carbon black, specifically carbon black color master batch, and the mass concentration of the carbon black is 30% -60%.
In the invention, the additive is one or more of long-chain ternary polyamide, silicone oil, organic silicon acrylate copolymer resin and gas-phase alumina; meanwhile, the conventional scratch-resistant silicone, PTFE, UHMWPE and the like in the plastic alloy field are selected, and compared with the modifier added in the invention.
At present, materials such as automobile interior instrument panels and steering wheels are painted by ABS, PC+ABS materials, the painting process is high in cost and environment-friendly, smell is large, the paint can be smeared after long-term hand touch, and the plastic ground color is leaked. The invention discloses a novel additive for preparing a spraying-free high-blackness and bright scratch-resistant PA alloy material for the first time, which unexpectedly improves the toughness of a product on the basis of effectively improving the scratch resistance and the wear resistance, and solves the problems that the existing scratch-resistant agent slightly improves the scratch resistance but reduces the toughness of the material; furthermore, the invention keeps the material qualified and resistant to grease, and solves the problem that the grease resistance of the material is reduced due to the scratch resistance in the prior art. Practical tests show that the technical scheme of the invention can meet the requirements of automotive interior materials.
Drawings
FIG. 1 is a photograph of a product prepared from particles of example 1 of the present invention.
Fig. 2 is a photograph of scratch resistance test of the product prepared from the particles of example 1.
FIG. 3 is a photograph of a wet abrasion resistance test of the product prepared from the particles of example 1.
Detailed Description
The invention discloses a spray-free high-blackness and bright scratch-resistant PA alloy material, which consists of transparent nylon resin, SAN resin, a compatilizer, an additive, a toughening agent, an auxiliary agent and carbon black. The preparation method of the spraying-free high-blackness and high-brightness scratch-resistant PA alloy material comprises the following steps of melt mixing transparent nylon resin, SAN resin, compatilizer, additive, toughening agent, auxiliary agent and carbon black to obtain the spraying-free high-blackness and high-brightness and high-scratch-resistant PA alloy material. According to the preparation method of the spraying-free high-blackness and bright scratch-resistant PA alloy material, raw materials can be directly fed into a double-screw extruder for extrusion and melt processing after being mixed, or single materials can be respectively added into an extruder through a weight-loss type metering scale, and an auxiliary agent, carbon black and the like are mixed together and are added through a single weight-loss type metering scale; the length-diameter ratio of the double-screw equipment is 30-50, the rotating speed is 300-1000 RPM, and the temperature can be 210-270 ℃ for processing, forming and granulating.
In the invention, the transparent nylon resin is long-chain copolymerized nylon, the transparency is more than 88 percent, the saturated water absorption is within 0.5 percent, the novel material TM156 of Shandong Guangdong boundary has small shrinkage, high size, good transparency, high coloring degree and lower saturated water absorption.
In the invention, the melt index of the SAN resin is 10-55g/10min,220 ℃ and 10kg; the mass content of AN is 25-35%. As AN example, NF2200 (AN content 26%): melt index 30g/10min (220 ℃ C. +10 kg); NX3400 (AN content 34%): melt index 12g/10min (220 ℃ C. +10 kg); NX3260 (AN content 31%): melt index 55g/10min (220 ℃ C. +10 kg); the manufacturer is the platform. SAN resin improves the grease resistance of PA resin, reduces the cost, and weakens the adverse effect on toughness through component matching.
In the invention, the compatilizer is a styrene-maleic anhydride-acrylonitrile terpolymer, and the manufacturer's Anhuixabeda ST-SAM4008; the toughening agent is a maleic anhydride grafted ethylene propylene diene monomer copolymer, and the U.S. is ceramic 3670; the auxiliary agent is the conventional components of the existing plastic alloy, such as the combination of common antioxidants, ultraviolet resistance agents and the like, and the antioxidant 1076 and the ultraviolet resistance agent CHIGUARD@1033 are selected in an experiment and mixed in equal mass; the carbon black is carrier-free carbon black, specifically a carbon black masterbatch, and the Ningbo masterbatch plant AS1040 is selected for experiments.
In the invention, the additive is long-chain ternary polyamide (Hidura polyamide 610) and organosilicon acrylic ester copolymer resin (Yuyaojihua SG 600A) which are compounded (mixed) according to the mass ratio of 3:7; meanwhile, the conventional scratch resistant agents such as silicone, PTFE, UHMWPE and the like in the plastic alloy field are selected as contrast agents, so that the technical progress of the added modifier is reflected.
The raw material components and the amounts of the examples and comparative examples are shown in Table 1, wherein the data are the amounts of the specific components in Kg.
Table 1 raw material components and amounts Kg of examples and comparative examples
After the raw materials in table 1 are mixed conventionally, the mixture is added into a double-screw extrusion melt processing, the length-diameter ratio of the double-screw equipment is 35, the rotating speed is 500 RPM, and the processing, forming and granulating are carried out at the temperature of 210-270 ℃ to obtain the spraying-free high-blackness and bright scratch-resistant PA alloy material.
Particles were routinely prepared as samples according to the test method.
The testing method of the material comprises the following steps:
cross scraping method: TL226-2018 3.7.3, using a hardness test pencil of 318, load 10N, ram diameter 0.75mm, allow for indentation, not scratch.
Wet abrasion: TL226-2018 3.7.6.1.3/refer to PV3906-2009, the diameter of a friction head is 16mm, the friction stroke is 101.6mm, the friction load is 9N, pure water is rubbed back and forth 100 times, and cotton friction white cloth with the thickness of 50 multiplied by 50mm is rubbed. The surface of the sample is at the level PV3906-2009 of less than or equal to 1, and the gray level of the color fastness of the wiping cloth is at least or equal to 4.
Gloss level: and (3) testing the injection molding sample of the same mold by adopting a glossiness meter under the normal temperature condition of 23+/-2 ℃, wherein the glossiness of the angle of 20 degrees is more than or equal to 78gloss according to the standard GB/T1743.
Appearance color: and (3) testing the injection molding sample of the same mold by adopting a color difference meter under the normal temperature condition of 23+/-2 ℃ and requiring the L value to be less than or equal to 24.6 (reaching the effect of high gloss black paint spraying visually).
Grease resistance: reference TL226-2018 3.7.6.3/PV3964-2006; covering the template with prescribed gauze, and smearing hand cream (Nivey deep moisturizing cream) on the upper half of the template to completely fill the holes of the gauze and remove redundant hand cream; the lower half of the template was coated with a sun cream (Niveya SPF 50) + ) Completely filling the pores of the gauze and removing the excessive sunscreen cream; placing it at high and lowAnd after the product is stored for 24 hours at 80 ℃ in a temperature test box, taking out the product, cooling the product for 15 minutes, washing off the sun cream/hand cream on the surface of the product, wiping the sample, and observing the appearance of the product. And then carrying out scratch resistance test: a hardness test bar type 318 was used, loaded with 10N, and the ram diameter was 0.75mm.
The requirements are: the color fastness gray level is more than or equal to 4; no change in appearance or feel (e.g., no fish tail, swelling, cracking, softening, cracking) as compared to the inspection state, the gloss is allowed to change slightly; scratch resistance tests allow for indentation and not scratch.
Notched impact strength: at normal temperature of 23+ -2deg.C, according to standard ISO 179-1eA.
The test results are shown in Table 2 below.
Table 2 test results for examples and comparative examples
FIG. 1 is a photograph of a product prepared from particles of example 1 of the present invention. Fig. 2 is a photograph of scratch resistance test of the product prepared from the particles of example 1. FIG. 3 is a photograph of a wet abrasion resistance test of the product prepared from the particles of example 1. The additive adopted by the invention is matched with the resin matrix and the toughening agent, so that the performance is improved, the surface glossiness of the product is more than 78gloss (20 DEG angle), the surface blackness reaches the blackness of high-gloss paint (L value is less than 24.6), and the notch impact strength is high; in particular, the additive of the invention unexpectedly improves the toughness of products on the basis of effectively improving the scratch resistance and the wear resistance, and solves the problems that the existing scratch resistance agent slightly improves the scratch resistance but reduces the toughness of materials; furthermore, the invention keeps the material qualified and resistant to grease, and solves the problem that the grease resistance of the material is reduced due to the scratch resistance in the prior art.
On the basis of comparative example 2, silicone, PTFE and the like were mixed in proportion as scratch resistant agents, and the scratch resistance of the obtained product was comparable, and toughness and grease resistance were not improved.
The additive of example 2 was replaced with an additive (group 1) in a low sliding friction coefficient self-lubricating TPV material as previously disclosed by the applicant in CN115873453a, and the experiment was found to be unsuitable and poor in product appearance.
Based on the embodiment 1, NF2200 or NX3400 is selected to replace NX3260, and the obtained product meets the requirements on grease resistance, scratch resistance and wet friction performance.
On the basis of the embodiment 1, the organosilicon acrylic ester copolymer resin is omitted, namely long-chain ternary polyamide (2.5) is adopted as an additive, so that scratch resistance and wet abrasion resistance of the product are hardly improved, and scratch is caused.
On the basis of example 1, long-chain ternary polyamide was omitted, namely, the silicone acrylate copolymer resin (2.5) was used as an additive, and after the injection molding of the prepared particles, the yield of the injection molded parts was reduced, and appearance defects were produced.
The existing commercial similar materials are used for preparing automobile interior instrument panels, steering wheels and the like, and are sprayed with ABS, PC+ABS materials, otherwise, the requirements of high blackness and brightness and scratch resistance cannot be met, the spraying process is high in cost, environment-friendly and large in smell, and the paint can be smeared after long-term hand touch, and the base color of plastics is leaked. The invention discloses a novel spraying-free high-blackness and bright scratch-resistant PA alloy material for the first time, and on the basis of effectively improving scratch resistance and wear resistance, the toughness of a product is unexpectedly improved, and the qualified grease resistance of the material is maintained. Practical tests show that the technical scheme of the invention can meet the requirements of automotive interior materials, and the alloy preparation process is simple and has high efficiency.
Claims (10)
1. The spray-free high-blackness and bright scratch-resistant PA alloy material is characterized by comprising transparent nylon resin, SAN resin, a compatilizer, an additive, a toughening agent, an auxiliary agent and carbon black.
2. The spray-free high-blackness and high-brightness scratch-resistant PA alloy material according to claim 1, wherein the mass sum of transparent nylon resin, SAN resin, compatilizer, additive, toughening agent, auxiliary agent and carbon black is 100%, and the mass sum is as follows:
65-85% of transparent nylon resin
SAN resin 5-25%
1-5% of compatilizer
Additive 2-7%
5 to 10 percent of toughening agent
1 to 2 percent of other processing aids
The balance of carbon black.
3. The spray-free high-blackness and high-brightness scratch-resistant PA alloy material according to claim 2, wherein,
70-80% of transparent nylon resin
SAN resin 5-15%
5-8% of compatilizer
Additive 2-3%
6 to 7 percent of toughening agent
1 to 2 percent of other processing aids
The balance of carbon black.
4. The spray-free high-blackness and high-brightness scratch-resistant PA alloy material according to claim 1, wherein the melt index of SAN resin is 10-55g/10min, and the mass content of AN is 25-35%; the compatilizer is styrene-maleic anhydride-acrylonitrile terpolymer; the toughening agent is a maleic anhydride grafted ethylene propylene diene monomer copolymer; the carbon black is unsupported carbon black.
5. The spray-free high-blackness and high-brightness scratch-resistant PA alloy material according to claim 1, wherein the additive is one or more of long-chain ternary polyamide, silicone oil, organosilicon acrylate copolymer resin and gas-phase alumina.
6. The preparation method of the spraying-free high-blackness and high-brightness scratch-resistant PA alloy material comprises the following steps of melt mixing transparent nylon resin, SAN resin, compatilizer, additive, toughening agent, auxiliary agent and carbon black to obtain the spraying-free high-blackness and high-brightness and high-scratch-resistant PA alloy material.
7. The use of the spray-free high-black-brightness scratch-resistant PA alloy material according to claim 1 for preparing a spray-free high-black-brightness scratch-resistant material.
8. The use according to claim 7, wherein the spray-free high-black-bright scratch-resistant material is a spray-free high-black-bright scratch-resistant automotive material.
9. The application of the additive in preparing the spray-free high-blackness and bright scratch-resistant PA alloy material according to claim 1, wherein the additive is one or more of long-chain ternary polyamide, silicone oil, organosilicon acrylate copolymer resin and gas-phase alumina.
10. The application of the additive in improving the scratch resistance and the grease resistance of the PA alloy material is characterized in that the additive is one or more of long-chain ternary polyamide, silicone oil, organosilicon acrylate copolymer resin and gas-phase alumina.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311729315.5A CN117683342A (en) | 2023-12-15 | 2023-12-15 | Spraying-free high-blackness and brightness scratch-resistant PA (polyamide) alloy material as well as preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311729315.5A CN117683342A (en) | 2023-12-15 | 2023-12-15 | Spraying-free high-blackness and brightness scratch-resistant PA (polyamide) alloy material as well as preparation method and application thereof |
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| Publication Number | Publication Date |
|---|---|
| CN117683342A true CN117683342A (en) | 2024-03-12 |
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| CN202311729315.5A Pending CN117683342A (en) | 2023-12-15 | 2023-12-15 | Spraying-free high-blackness and brightness scratch-resistant PA (polyamide) alloy material as well as preparation method and application thereof |
Country Status (1)
| Country | Link |
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| CN (1) | CN117683342A (en) |
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