CN112430393B - Ultraviolet-resistant thermoplastic polyamide composite material for laser welding and preparation method thereof - Google Patents
Ultraviolet-resistant thermoplastic polyamide composite material for laser welding and preparation method thereof Download PDFInfo
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- CN112430393B CN112430393B CN202011314967.9A CN202011314967A CN112430393B CN 112430393 B CN112430393 B CN 112430393B CN 202011314967 A CN202011314967 A CN 202011314967A CN 112430393 B CN112430393 B CN 112430393B
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- 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
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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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C08K5/20—Carboxylic acid amides
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
- C08K5/3475—Five-membered rings condensed with carbocyclic rings
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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Abstract
The invention provides an ultraviolet-resistant thermoplastic polyamide composite material for laser welding and a preparation method thereof, and relates to the technical field of composite materials. An ultraviolet-resistant thermoplastic polyamide composite material for laser welding comprises 40-95% of thermoplastic polyamide, 0.1-5% of black dye, 0.05-1% of first light stabilizer, 0.05-1% of second light stabilizer, 0.05-0.5% of antioxidant, 0.1-2% of release agent and 5-50% of glass fiber. The material has the characteristics of slow fading under ultraviolet exposure and high laser transmittance. A method of making an ultraviolet resistant thermoplastic polyamide composite material for laser welding, comprising: mixing thermoplastic polyamide, black dye, a first light stabilizer, a second light stabilizer, an antioxidant, a mold release agent and glass fiber, and extruding and granulating the mixture by an extruder at the granulation temperature of 240-320 ℃. The method is simple and convenient to operate, strong in controllability and suitable for large-scale production.
Description
Technical Field
The invention relates to the technical field of composite materials, and particularly relates to an ultraviolet-resistant thermoplastic polyamide composite material for laser welding and a preparation method thereof.
Background
Laser welding has been rapidly developed in recent years as an emerging welding method. Compared with traditional vibration welding, friction welding and ultrasonic welding, the laser welding has the advantages of high production efficiency, no generation of powder, capability of performing 3D welding and the like. Due to the above advantages, laser welding is a new mainstream welding method in a camera manufacturing process required for automatic driving. Polyamide is a widely used camera housing material. Laser welding materials cannot be dyed with carbon black to achieve the laser transmission effect, and only organic toners that do not absorb infrared laser light can be used. However, the organic toner has poor ultraviolet stability, and can fade after long-time outdoor use, so that the color of the product appearance is changed, and the user experience is influenced. The invention provides an ultraviolet-resistant laser transmission scheme, which can realize better ultraviolet stability and high laser transmission rate at the same time.
Disclosure of Invention
The invention aims to provide an ultraviolet-resistant thermoplastic polyamide composite material for laser welding, which has better ultraviolet stability and high laser transmittance.
The invention also aims to provide a preparation method of the ultraviolet-resistant thermoplastic polyamide composite material for laser welding, which is simple and convenient to operate, strong in controllability and suitable for large-scale production.
The technical problem to be solved by the invention is realized by adopting the following technical scheme:
the invention provides an ultraviolet-resistant thermoplastic polyamide composite material for laser welding, which comprises the following components in percentage by weight:
40 to 95 percent of thermoplastic polyamide, 0.1 to 5 percent of black dye, 0.05 to 1 percent of first light stabilizer, 0.05 to 1 percent of second light stabilizer, 0.05 to 0.5 percent of antioxidant, 0.1 to 2 percent of release agent and 5 to 50 percent of glass fiber.
Further, in preferred embodiments of the invention, the polyamide is nylon 6, nylon 66, nylon 610, nylon 6T copolymer, nylon 9T, nylon 10T, MXD-6, and mixtures thereof.
Further, in a preferred embodiment of the present invention, the ultraviolet resistant thermoplastic polyamide composite material for laser welding is characterized in that the content of the black dye is 0.5 to 2%.
Further, in a preferred embodiment of the present invention, the ultraviolet-resistant thermoplastic polyamide composite material for laser welding is characterized in that the ratio of the first light stabilizer to the second light stabilizer is 1.
Further, in a preferred embodiment of the invention, the ultraviolet-resistant thermoplastic polyamide composite material for laser welding is characterized in that the material also contains acetate, and the content of the acetate is 0.2-2%.
The invention provides a preparation method of an ultraviolet-resistant thermoplastic polyamide composite material for laser welding, which comprises the following steps: mixing thermoplastic polyamide, a first light stabilizer, a second light stabilizer, an antioxidant, a mold release agent and glass fiber, and extruding and granulating the mixture by an extruder at the granulation temperature of 240-320 ℃.
Preferably, the preparation method of the ultraviolet resistant thermoplastic polyamide composite material for laser welding of the present invention comprises:
40 to 95 percent of thermoplastic polyamide, 0.1 to 5 percent of black dye, 0.05 to 1 percent of first light stabilizer, 0.05 to 1 percent of second light stabilizer, 0.05 to 0.5 percent of antioxidant, 0.1 to 2 percent of release agent and 5 to 50 percent of glass fiber are mixed according to weight percentage and extruded and granulated by an extruder, wherein the granulation temperature is 240 to 320 ℃.
The ultraviolet-resistant thermoplastic polyamide composite material for laser welding and the preparation method thereof have the beneficial effects that:
the invention adopts the combined action of the thermoplastic polyamide, the first light stabilizer, the second light stabilizer, the antioxidant, the release agent and the glass fiber, and has better ultraviolet stability and high laser transmittance. The preparation method is simple and feasible, and is suitable for large-scale production and application.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The ultraviolet-resistant thermoplastic polyamide composite material for laser welding and the preparation method thereof according to the embodiments of the present invention will be described in detail below.
The features and properties of the present invention are described in further detail below with reference to examples. The following raw materials were used in the examples: PA66 is Neumann EPR24, PA6 is Basv Ultramid B3L, PA6I/6T is DuPont Selar3426, the Black dye 1 is Basv Lumogen K0088, the Black dye 2 is PLSV Polysolve Black 3, the first photostabilizer is Cyanot UV5411, the second photostabilizer is Basv Tinuvin 880, the Red dye is Langshen Red E2G, and the Green dye is Langshen Green 5B Gran. The other raw materials are all common raw materials sold in the market.
Example 1
According to the weight percentage, all the components are granulated by a double-screw extruder according to the proportion in the table 1, and the granulation temperature is 240-280 ℃. The obtained particles were subjected to testing of notched impact strength, tensile strength, laser transmittance (1064 nm) at a thickness of 2mm after injection molding, and gray level at the initial state and after ultraviolet aging for a certain period of time. Wherein the ultraviolet aging adopts the aging condition of ISO4892-2, and the other testing methods are all ISO standard testing methods.
Table 1 different dye Performance data
As can be seen from the data in Table 1, the product showed significant discoloration upon UV aging for 750h, whether using red green or black dye. In the automobile industry, the minimum requirement is that the gray scale of 750 hours is more than or equal to 4, and the higher requirement is that the gray scale of 1000 hours is more than 4. It can be seen that neither the red-green dye nor the black dye 2 can meet the requirements, and when the content of the black dye 1 is higher, although the fading is smaller than that of the red-green dye and the black dye 2, the requirement of 750 hours cannot be met. Meanwhile, when the content of the black dye 2 exceeds 2%, the impact performance of the material is obviously reduced.
Example 2
According to the weight percentage, all the components are granulated by a double-screw extruder according to the proportion in the table 2, and the granulation temperature is 240-280 ℃. The obtained particles were subjected to testing of notched impact strength, tensile strength, laser transmittance (1064 nm) at a thickness of 2mm after injection molding, and gray level at the initial state and after ultraviolet aging for a certain period of time. Wherein the ultraviolet aging adopts the aging condition of ISO4892-2, and the other testing methods are all ISO standard testing methods.
TABLE 2 light stabilizer Performance data
In example 2, it can be seen that when the black dye 2 is compounded with the light stabilizer 1 and the light stabilizer 2, the ultraviolet fading resistance of the material is obviously improved, and particularly when the two light stabilizers are added according to a certain proportion (sample 7 and sample 8), the improvement is more obvious, and the requirement that the 750h gray scale is greater than or equal to 4 can be realized. When a light stabilizer is added separately, the ultraviolet resistance of the material is not changed. Meanwhile, the ultraviolet resistance of the red-green dye and the black dye 2 is not changed even if the compounded light stabilizer is added. The ultraviolet resistance is improved, and simultaneously, the impact property, the tensile strength and the laser transmittance of the material are not obviously reduced.
Example 3
According to the weight percentage, all the components are granulated by a double-screw extruder according to the proportion in the table 3, and the granulation temperature is 240-280 ℃. The obtained particles were subjected to testing of notched impact strength, tensile strength, laser transmittance (1064 nm) at a thickness of 2mm after injection molding, and gray level at the initial state and after ultraviolet aging for a certain period of time. Wherein the ultraviolet aging adopts the aging condition of ISO4892-2, and the rest test methods are all ISO standard test methods.
TABLE 3 data for polyamide blends
It can be seen from the data in table 3 that this combination of black dye 1 and two light stabilizers is equally applicable to PA6, as well as to blended systems of PA 66. Especially, when PA6I/6T and sodium acetate exist in the system, the laser transmittance of the material is greatly improved, and the material also has good ultraviolet resistance.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (3)
1. An ultraviolet resistant thermoplastic polyamide composite material for laser welding, characterized by comprising, in weight percent:
0.5 to 2 percent of black dye, 40 to 69.4 percent of thermoplastic polyamide, 0.05 to 1 percent of first light stabilizer, 0.05 to 1 percent of second light stabilizer, 0.05 to 0.5 percent of antioxidant, 0.1 to 2 percent of release agent and 5 to 50 percent of glass fiber;
wherein the black dye is a black dye containing a perylene structure, the first light stabilizer is a benzotriazole light stabilizer, and the second light stabilizer is a hindered amine light stabilizer;
the weight ratio of the first light stabilizer to the second light stabilizer is 1 to 1; the material also contains 0.2-2% by weight of acetate.
2. The ultraviolet resistant thermoplastic polyamide composite material for laser welding of claim 1 wherein the thermoplastic polyamide is nylon 6, nylon 66, nylon 610, nylon 6T copolymer, nylon 9T, nylon 10T, MDX6 or mixtures thereof.
3. A process for the preparation of a uv-resistant thermoplastic polyamide composite material for laser welding according to any one of claims 1 to 2, characterized in that it comprises: mixing the thermoplastic polyamide, the black dye, the first light stabilizer, the second light stabilizer, the antioxidant, the release agent, the glass fiber and the acetate, and extruding and granulating the mixture by an extruder at the granulation temperature of 240-320 ℃.
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| CN202011314967.9A CN112430393B (en) | 2020-11-20 | 2020-11-20 | Ultraviolet-resistant thermoplastic polyamide composite material for laser welding and preparation method thereof |
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| CN202011314967.9A CN112430393B (en) | 2020-11-20 | 2020-11-20 | Ultraviolet-resistant thermoplastic polyamide composite material for laser welding and preparation method thereof |
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| CN112430393B true CN112430393B (en) | 2022-11-18 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6110566A (en) * | 1997-10-23 | 2000-08-29 | 3M Innovative Properties Company | Stabilization of fluorescent dyes in vinyl articles using hindered amine light stabilizers |
| US6472050B1 (en) * | 1999-12-30 | 2002-10-29 | Avery Dennison Corporation | Light stable fluorescent vinyl suitable for use as a highway retroreflective roll-up sign |
| ZA200301683B (en) * | 2002-03-04 | 2004-09-06 | Ciba Sc Holding Ag | Synergistic combinations of UV absorbers for pigmented polyolefins. |
| EP3913016A4 (en) * | 2019-01-18 | 2022-11-09 | Mitsubishi Engineering-Plastics Corporation | Resin composition, molded article, kit, and method for producing molded article |
| CN111320867B (en) * | 2019-12-24 | 2023-01-10 | 广州辰东新材料有限公司 | Polyamide composite material and preparation method and application thereof |
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